CN101160381A - Polyalphaolefin & fischer-tropsch derived lubricant base oil lubricant blends - Google Patents
Polyalphaolefin & fischer-tropsch derived lubricant base oil lubricant blends Download PDFInfo
- Publication number
- CN101160381A CN101160381A CNA2006800124169A CN200680012416A CN101160381A CN 101160381 A CN101160381 A CN 101160381A CN A2006800124169 A CNA2006800124169 A CN A2006800124169A CN 200680012416 A CN200680012416 A CN 200680012416A CN 101160381 A CN101160381 A CN 101160381A
- Authority
- CN
- China
- Prior art keywords
- base oil
- blending
- lubricant base
- finished lubricants
- fischer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000314 lubricant Substances 0.000 title claims abstract description 418
- 239000002199 base oil Substances 0.000 title claims abstract description 257
- 229920013639 polyalphaolefin Polymers 0.000 title claims abstract description 81
- 239000000203 mixture Substances 0.000 title claims description 23
- 125000003118 aryl group Chemical group 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 57
- 238000002156 mixing Methods 0.000 claims description 140
- 239000000654 additive Substances 0.000 claims description 68
- 230000000996 additive effect Effects 0.000 claims description 62
- 230000003449 preventive effect Effects 0.000 claims description 49
- 239000003921 oil Substances 0.000 claims description 47
- 238000012360 testing method Methods 0.000 claims description 45
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 39
- 239000010705 motor oil Substances 0.000 claims description 30
- 239000007800 oxidant agent Substances 0.000 claims description 22
- 150000001924 cycloalkanes Chemical class 0.000 claims description 19
- 239000005864 Sulphur Substances 0.000 claims description 16
- 238000002485 combustion reaction Methods 0.000 claims description 16
- -1 sulphur compound Chemical class 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000000446 fuel Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 239000002283 diesel fuel Substances 0.000 claims description 7
- 230000001050 lubricating effect Effects 0.000 claims description 6
- 230000007246 mechanism Effects 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000006184 cosolvent Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
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- 239000011733 molybdenum Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 claims description 4
- 239000003502 gasoline Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- SCJNCDSAIRBRIA-DOFZRALJSA-N arachidonyl-2'-chloroethylamide Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(=O)NCCCl SCJNCDSAIRBRIA-DOFZRALJSA-N 0.000 claims description 3
- 239000004519 grease Substances 0.000 claims description 3
- 239000003879 lubricant additive Substances 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000005069 Extreme pressure additive Substances 0.000 claims description 2
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 claims description 2
- ZGRWZUDBZZBJQB-UHFFFAOYSA-N benzenecarbodithioic acid Chemical class SC(=S)C1=CC=CC=C1 ZGRWZUDBZZBJQB-UHFFFAOYSA-N 0.000 claims description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 239000010725 compressor oil Substances 0.000 claims description 2
- 235000009508 confectionery Nutrition 0.000 claims description 2
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- 239000006185 dispersion Substances 0.000 claims description 2
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- 229910001463 metal phosphate Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
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- 150000008301 phosphite esters Chemical class 0.000 claims description 2
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- 239000002808 molecular sieve Substances 0.000 description 22
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 22
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- 239000007789 gas Substances 0.000 description 13
- 230000001590 oxidative effect Effects 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
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- 150000002431 hydrogen Chemical class 0.000 description 5
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
- C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/02—Well-defined hydrocarbons
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/17—Fisher Tropsch reaction products
- C10M2205/173—Fisher Tropsch reaction products used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/042—Metal salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/043—Ammonium or amine salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/049—Phosphite
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/74—Noack Volatility
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/12—Gas-turbines
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
- C10N2040/253—Small diesel engines
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
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- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
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Abstract
Blended lubricant base oils and blended finished lubricants comprising = 70 weight percent Fischer-Tropsch derived lubricant base oils comprising = 6 weight % molecules with monocycloparaffmic functionality and less than 0.05 weight % molecules with aromatic functionality; at least one polyalphaolefin lubricant base oil with a kinematic viscosity at 100 DEG C greater than about 30 cSt and less than 150 cSt are provided. These blended lubricant base oils and blended finished lubricants exhibit superior friction and wear properties, in addition to other highly desired properties. Also provided are processes for making these blended lubricant base oils and blended finished lubricants.
Description
The present invention relates to comprise the lubricant of blending of Fischer-tropsch derived lubricant base oil and at least a polyalphaolefin lubricant base oil and the finished lubricants of blending, and the method for preparing them.In order to realize acceptable wear resistance, the finished lubricants of this blending is surprisingly than the Fischer-tropsch derived lubricant base oil requirement wear preventive additive still less that does not contain at least a polyalphaolefin (PAO) lubricant base oil.
Background technology
Need high performance automobile and industrial lubricants.Therefore, lubricant manufacturers must provide the finished lubricants that shows high performance character.In order to produce these finished lubricants, higher-quality lubricant base oil concoction raw material is being sought by lubricant manufacturers.Important use properties comprises additive solubleness, settling control and oilness.
The source that is increasing of these high-quality lubricant base oil concoction raw materials is synthetic lubricants.Synthetic lubricant comprises Fischer-tropsch derived lubricant base oil and polyalphaolefin.Polyalphaolefin is the synthetic lubricant base oil of producing by the chemical polymerization method.Yet the production of these lubricant base oils is expensive.In the work of seeking high performance lubricant, concentrate on Fischer-tropsch derived lubricant recently.Although Fischer-tropsch derived lubricant base oil is because of the low levels of its biodegradable and undesirable impurity such as sulphur but ideal, Fischer-tropsch derived lubricant does not have wear resistance, oilness and the deposition properties of hope usually.Although by using additive to improve these use propertieies is well-known in the art, these additives cost normally expensive and that therefore may increase lubricant base oil significantly.In addition, worldwide manufacturers of engines is being considered will provide safety margin to the low sulphur of engine oil and additive and phosphorus restriction to the operation of aftertreatment hardware because it is believed that these restrictions.Wear preventive additive contains a large amount of sulphur and phosphorus usually.Therefore, wish to produce the lubricant base oil that has high use properties under the situation of expensive additive or have the additive that contains sulphur and phosphorus of reduction not having to use in a large number.
It is well known in the art producing synthetic lubricant, and has in production and a lot of experimental trials have been arranged aspect the synthetic lubricant of high use properties.For example, United States Patent (USP) 6,008, No. 164, United States Patent (USP) 6,080, the method that No. 301, No. 6,165,949, United States Patent (USP), WO 00/14188, WO 02/064710A2, WO 02/064711A1, WO 02/070629A1 and WO 02/070636A1 relate to the synthetic lubricant composition and produce the lubrication base oil plant.
For the oil base stock of hydrocracking and the character of polyalphaolefin research is arranged also.V.J.Gatto etc. are published in synthetic lubricated magazine 19-1 phase 3-18 page or leaf of in April, 2002 " chemical structure to the oil base stock of hydrocracking and the physical properties of polyalphaolefin and the influence of antioxidant response " [" The influence of chemical structure on the physicalproperties and antioxidant response of hydrocracked base stocksand polyalphaolefins ", by V.J.Gatto et.al., J.SyntheticLubrication 19-1, April 2002 (19), 3-18] the oil base stock chemical constitution of hydrocracking is disclosed to lubricant properties, the influence of oxidation susceptibility and antioxidant addn response.In this research, analyzed the oil base stock and the polyalphaolefin of 15 kinds of hydrocracking.
Although synthetic lubricant has been carried out above research, still need to comprise the synthetic lubricant of Fischer-tropsch derived lubricant base oil, this ucon oil shows high-performance (friction and the abrasion resisting character that comprise improvement), realizes this high-performance and need not to add a large amount of additives.
Summary of the invention
Have been found that the lubricant base oil of the blending of the present invention that comprises Fischer-tropsch derived lubricant base oil and polyalphaolefin and the finished lubricants of blending show the friction and the abrasion resisting character of improvement, adopt the wear preventive additive of reduction.
In one embodiment, the present invention relates to the lubricant base oil concocted.The lubricant base oil of blending of the present invention comprises: the Fischer-tropsch derived lubricant base oil of 〉=70wt%, it comprises 〉=6wt% have that mononaphthene belongs to the molecule of functionality and less than the molecule of 0.05wt% with aromatic functionality; With at least a polyalphaolefin lubricant base oil, its 100 ℃ kinematic viscosity greater than about 30cSt and less than 150cSt.
In another embodiment, the present invention relates to the finished lubricants concocted.The finished lubricants of described blending comprises: the Fischer-tropsch derived lubricant base oil of 〉=70wt%, it comprises 〉=6wt% have that mononaphthene belongs to the molecule of functionality and less than the molecule of 0.05wt% with aromatic functionality; At least a polyalphaolefin lubricant base oil, its 100 ℃ kinematic viscosity greater than about 30cSt and less than 150cSt; At least a wear preventive additive with significant quantity.
In another embodiment, the method for the oil engine that comprises valve mechanism of the present invention relates to turn round.This method comprises the finished lubricants lubricating engine that uses the fuels run engine and use blending, the finished lubricants of described blending comprises: the Fischer-tropsch derived lubricant base oil of 〉=70wt%, it comprises 〉=6wt% have that mononaphthene belongs to the molecule of functionality and less than the molecule of 0.05wt% with aromatic functionality; At least a polyalphaolefin lubricant base oil, its 100 ℃ kinematic viscosity greater than about 30cSt and less than 150cSt; At least a wear preventive additive with significant quantity.
In another embodiment, the present invention relates to reduce the method for the wearing and tearing in the iron alloy equipment.This method comprises with the lubricated described equipment of the finished lubricants of blending, with the described equipment that turns round in described lubricated back, the finished lubricants of wherein said blending comprises: the Fischer-tropsch derived lubricant base oil of 〉=70wt%, it comprises 〉=6wt% have that mononaphthene belongs to the molecule of functionality and less than the molecule of 0.05wt% with aromatic functionality; At least a polyalphaolefin lubricant base oil, its 100 ℃ kinematic viscosity greater than about 30cSt and less than 150cSt; At least a wear preventive additive with significant quantity.
Detailed Description Of The Invention
Finished lubricants comprises at least a lubricant base oil and at least a additive.Lubricant base oil is the most important component of finished lubricants, generally account for finished lubricants greater than 70%.Finished lubricants can be used to automobile, diesel engine, wheel shaft, wheel box and industrial application.Finished lubricants must satisfy by the specification of relevant NGO at their intended application defined.
Fischer-tropsch derived lubricant base oil is to the base oil of small part derived from Fischer-tropsch process.According to the present invention, the lubricant of described blending comprise at least a comprising 〉=6wt% have that mononaphthene belongs to the molecule of functionality and less than the Fischer-tropsch derived lubricant base oil of the molecule of 0.05wt% and at least a kinematic viscosity at 100 ℃ with aromatic functionality greater than about 30cSt and less than the polyalphaolefin lubricant base oil of 150cSt.The finished lubricants of blending of the present invention comprises: at least a Fischer-tropsch derived lubricant base oil, it comprises 〉=6wt% have that mononaphthene belongs to the molecule of functionality and less than the molecule of 0.05wt% with aromatic functionality; At least a polyalphaolefin lubricant base oil, its 100 ℃ kinematic viscosity greater than about 30cSt and less than 150cSt; At least a wear preventive additive with significant quantity.The finished lubricants of blending of the present invention shows superior friction and abrasion resisting character.Preferably, the lubricant base oil of described blending comprises 〉=the Fischer-tropsch derived lubricant base oil of 70wt%.
Usually, the significant quantity of needed wear preventive additive is lower than needed amount in the finished lubricants that is comprising traditional petroleum lubricant base oil or polyalphaolefin lubricant base oil in the finished lubricants that comprises Fischer-tropsch derived lubricant base oil.According to the present invention, surprisingly find, the finished lubricants that does not contain the polyalphaolefin lubricant base oil with comprising Fischer-tropsch derived lubricant base oil is compared, comprise with the Fischer-tropsch derived lubricant base oil of polyalphaolefin lubricant base oil (its 100 ℃ kinematic viscosity greater than about 30cSt and less than 150cSt) blending (it comprises 〉=6wt% have that mononaphthene belongs to the molecule of functionality and less than the molecule of 0.05wt% with aromatic functionality) the remarkable wear preventive additive still less of finished lubricants needs.Correspondingly, in the finished lubricants of blending of the present invention, need the wear preventive additive of reduction.Therefore, the lubricant of blending of the present invention can be used for preparing high quality machine oil and other finished lubricants that satisfies the strictest modern machine oil specification.
The significant quantity of at least a wear preventive additive is the amount that wear volume is reduced by at least the wear preventive additive of 1,000 cu under the plane of instigating when there is not described additive in the wear volume ratio under HFRR test midplane of the present invention.Preferably, the significant quantity of at least a wear preventive additive is meant, have under the load that 1000g applies less than 460 in order to provide, 000 cu, preferably less than 350, (High FrequencyReciprocating Rig, the HFRR) finished lubricants of wear volume under the plane is in additive-package or join the amount of the wear preventive additive in the lubricant base oil of described blending separately for the high frequency reciprocating apparatus of 000 cu.According to the present invention, the significant quantity of preferred at least a wear preventive additive is the 0.001-5wt% of the finished lubricants of described blending.In the finished lubricants of blending of the present invention, the significant quantity of wear preventive additive is less than comprising the Fischer-tropsch derived lubricant base oil with preferred composition of the present invention but be not contained in 100 ℃ kinematic viscosity greater than about 30cSt and less than the significant quantity of desired wear preventive additive in the finished lubricants of the polyalphaolefin lubricant base oil of 150cSt.In the finished lubricants of blending of the present invention, the significant quantity of wear preventive additive is lower than the kinematic viscosity that is included in 100 ℃ greater than about 30cSt and less than the polyalphaolefin lubricant base oil of 150cSt but do not conform to the significant quantity of desired wear preventive additive in the lubricant of Fischer-tropsch derived lubricant base oil of the present invention.
Many finished lubricants specifications are included in the restriction of wearing and tearing aspect.The example of specification that is included in the test limits of wearing and tearing aspect is: API bus engine test approaches SJ and SL; The ACEA2002 Europe oil product sequence that is used for petrol engine, light-duty diesel engine and heavy duty diesel engine; ASTM D4950 lubricating grease kind; Cincinnati-Milacron P-68 hydraulic fluid specification; With General Motors C-4 automatic gear-box fluid specification.
The lubricant of described blending of the present invention and the finished lubricants of described blending are included in 100 ℃ of kinematic viscosity greater than about 30cSt and less than the polyalphaolefin lubricant base oil of 150cSt.This polyalphaolefin lubricant base oil can be commercially available, perhaps as Shubkin, Ronald L. (1993) Polyalphaolefins, Synthetic Lubricants andHigh-Performance Functional Fluids and Pernik, Mark G. (2002) Polyalphaolefins, coming described in the STLE Annual Meeting, Houston TX, SyntheticLubricants Course is synthetic.Can be commercially available 100 ℃ kinematic viscosity greater than about 30cSt and less than the polyalphaolefin base of 150cSt from many manufacturerss, described manufacturers comprises Chevron Phillips, British Petroleum and ExxonMobil.
The lubricant base oil of described blending of the present invention and the finished lubricants of described blending comprise Fischer-tropsch derived lubricant base oil, this Fischer-tropsch derived lubricant base oil comprises 〉=6wt% have a molecule that mononaphthene belongs to functionality, preferred 8wt% has a molecule that mononaphthene belongs to functionality, even more preferably 〉=10wt% have a molecule that mononaphthene belongs to functionality.
The lubricant base oil of described blending of the present invention and the finished lubricants of described blending comprise Fischer-tropsch derived lubricant base oil, this Fischer-tropsch derived lubricant base oil comprises the very molecule with aromatic functionality of low weight percentage, high weight percent have a molecule that cycloalkanes belongs to functionality, with high have mononaphthene belong to functionality molecule weight percent with have polynaphthene belong to functionality molecule weight percent ratio (or high weight percent have mononaphthene belong to the molecule of functionality and very low weight percentage have a molecule that polynaphthene belongs to functionality), as the U.S.S.N.10/744389 that submits on December 23rd, 2003, the U.S.S.N.10/743 that the U.S.S.N.10/744870 that on December 23rd, 2003 submitted to and on December 23rd, 2003 submit to, described in 932, by reference described document integral body is attached to herein.
In a preferred embodiment, the lubricant base oil of described blending of the present invention and the finished lubricants of described blending comprise Fischer-tropsch derived lubricant base oil, this Fischer-tropsch derived lubricant base oil comprises the molecule with aromatic functionality less than 0.05wt%, the molecule that cycloalkanes belongs to functionality that has greater than 10wt%, with high have mononaphthene belong to functionality molecule weight percent with have polynaphthene and belong to the ratio of weight percent of the molecule of functionality, be preferably greater than 15.In another preferred embodiment, the lubricant base oil of described blending of the present invention and the finished lubricants of described blending comprise Fischer-tropsch derived lubricant base oil, this Fischer-tropsch derived lubricant base oil comprises less than 0.01wt%, is more preferably less than the molecule with aromatic functionality of 0.008wt%.
By comprising the method for hydroisomerization, prepare the Fischer-tropsch derived lubricant base oil that mononaphthene belongs to the molecule of functionality that has of described comprising 〉=6wt% from the waxy fraction of Fischer-Tropsch synthetic crude.The described Fischer-tropsch derived lubricant base oil of the lubricant that is used to concoct by the method preparation that comprises following step and the finished lubricants of blending: it is synthetic so that product stream to be provided to carry out Fischer-Tropsch; From this product stream, isolate the wax stock of alkane genus basically; This wax stock of belonging to of alkane basically of hydroisomerization; The separating isomerism change oil; Randomly this isomerization of hydrofining oil.Isolate from described method comprise 〉=6wt% have that mononaphthene belongs to the molecule of functionality and less than the Fischer-tropsch derived lubricant base oil of the molecule of 0.05wt% with aromatic functionality.Also can isolate the Fischer-tropsch derived lubricant base oil of above-mentioned preferred embodiment from described method.Preferably, use the wax stock that the described alkane basically of shape mesoporous molecular sieve hydroisomerization under the condition of about 600-750 belongs to of selecting that comprises the noble metal hydrogenation component.The preferred method that is used to prepare described Fischer-tropsch derived lubricant base oil is described in the U.S.S.N.10/744 that submitted on December 23rd, 2003, the U.S.S.N.10/744 that on December 23rd, 389 and 2003 submitted to, in 870, by reference its integral body is attached to herein.
According to the present invention, wish that the lubricant base oil of described blending and the finished lubricants of described blending comprise Fischer-tropsch derived lubricant base oil, this Fischer-tropsch derived lubricant base oil contains the molecule that cycloalkanes belongs to functionality that has of high weight percent, because naphthenic hydrocarbon is given additive solvability and elastomer compatibility.Wish that also the lubricant base oil of blending and the finished lubricants of blending comprise Fischer-tropsch derived lubricant base oil, this Fischer-tropsch derived lubricant base oil have very high have mononaphthene belong to functionality molecule weight percent with have polynaphthene and belong to the ratio (or high weight percent have the molecule that polynaphthene belongs to functionality that has that mononaphthene belongs to the molecule of functionality and utmost point low weight percentage) of weight percent of the molecule of functionality, because have the molecule reduction oxidative stability that polynaphthene belongs to functionality, reduce viscosity index and increase the Noack volatility.Be published in " chemical structure to the oil base stock of hydrocracking and the physical properties of polyalphaolefin and the influence of antioxidant response " [V.J.Gatto et al in April, 2002 " synthetic lubricated magazine " the 19-1 phase 3-18 page or leaf at V.J.Gatto etc., " Theinfluence of chemical structure on the physical properties andantioxidant response of hydrocracked base stocks andpolyal phaolefins ", J.Synthetic Lubrication 19-1, April 2002, pp3-18] in, provided and had the model of influence that polynaphthene belongs to the molecule of functionality.
The lubricant of blending of the present invention comprises 70 to about 99wt% Fischer-tropsch derived lubricant base oil and about 1 to the polyalphaolefin lubricant base oil less than 30wt%.The finished lubricants of blending of the present invention comprises the polyalphaolefin lubricant base oil of the Fischer-tropsch derived lubricant base oil of the about 99wt% of 70-, about 1-30wt% and one or more wear preventive additives of 0.001-5wt%.Preferably, described finished lubricants comprises one or more wear preventive additives of 0.001-4wt%.
Definition
In whole specification sheets, will use following term, and except as otherwise noted, they will have following implication.
Term " derived from Fischer-tropsch process " or " Fischer-tropsch derived " be meant described product, cut or raw material stem from Fischer-tropsch process or a certain stage by Fischer-tropsch process production.
Aromatic group is meant and contains at least one group of any hydrocarbon materialization compound or the group of sharing the atom of continual delocalized electron cloud, and wherein the number of delocalized electron meets the Huckel rule (for example, 6 electronics are arranged during n=1, etc.) of 4n+2 in this group atom.Representational example includes but not limited to benzene, biphenyl, naphthalene etc.
Molecule with aromatic functionality is meant and anyly is the molecule of aromatic group or contains one or more aromatic groups as substituent molecule.
Have molecule that cycloalkanes belongs to functionality and be meant that any is that the molecule of stable hydrocarbon group of monocycle or fused polycycle or the stable hydrocarbon group that contains one or more monocycles or fused polycycle are as substituent molecule.Described cycloalkanes belongs to group can be randomly by one or more, and preferred 1-3 substituting group replaces.Representational example includes but not limited to cyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, suberyl, perhydronaphthalene, octahydro pentalene, (pentadecane-6-yl) hexanaphthene, 3,7,10-thricyclohexyl pentadecane, 1-(pentadecane-6-yl) perhydronaphthalene etc.
Have molecule that mononaphthene belongs to functionality be meant 3-7 ring carbon the monocyclic saturated hydrocarbon group base any molecule or by any molecule of the monocyclic saturated hydrocarbon group base replacement of one 3-7 ring carbon.Described cycloalkanes belongs to group can be randomly by one or more, and preferred 1-3 substituting group replaces.Representational example includes but not limited to cyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, suberyl, (pentadecane-6-yl) hexanaphthene etc.
Have the molecule that polynaphthene belongs to functionality and be meant that any is the molecule of the fused polycycle stable hydrocarbon cyclic group of two or more fused rings, any molecule that is replaced by one or more fused polycycle stable hydrocarbon cyclic groups of forming by two or more fused rings, or any quilt is more than the molecule of the monocyclic saturated hydrocarbon group base replacement of one 3-7 ring carbon.Described fused polycycle stable hydrocarbon cyclic group is two fused rings preferably.Described cycloalkanes belongs to group can be randomly by one or more, and preferred 1-3 substituting group replaces.Representational example includes but not limited to perhydronaphthalene, octahydro pentalene, 3,7,10-thricyclohexyl pentadecane, 1-(pentadecane-6-yl) perhydronaphthalene etc.
" compressed ignition internal combustion engine " is meant diesel motor.
" oil engine " is the engine such as automobile gasoline piston engine or diesel engine, and wherein fuel is in internal combustion of engine own rather than externally stove burning (as in steam engine).These engines comprise natural gas engine, diesel motor and petrol engine.They can be two strokes or four-stroke.
" many grades crank case of internal combustion engine oil " is the lubricant that satisfies the SAE J300 specification in June calendar year 2001.API is with the SAE viscosity grade classification of engine oil according to them.Following Table I has been summarized described classification.
Table I: API engine oil classification
| The SAE viscosity grade | Maximum cold-starting viscosity, cP | The maximum temperature pumping viscosity of no yielding stress, cP | At 100 ℃ minimum low shear rate kinematic viscosity, cSt | At 100 ℃ maximum low shear rate kinematic viscosity, cSt | At 150 ℃ minimum high shear rate viscosity, cP |
| 0W-_ | 6200，-35℃ | 60000，-40℃ | 3.8 | - | - |
| 5W-_ | 6600，-30℃ | 60000，-35℃ | 3.8 | - | - |
| 10W-_ | 7000，-25℃ | 60000，-30℃ | 4.1 | - | - |
| 15W-_ | 7000，-20℃ | 60000，-25℃ | 5.6 | - | - |
| 20W-_ | 9500，-15℃ | 60000，-20℃ | 5.6 | - | - |
| 25W-_ | 13000，-10℃ | 60000，-15℃ | 9.3 | - | - |
| _W-20 | - | - | 5.6 | 9.3 | 2.6 |
| _W-30 | - | - | 9.3 | 12.5 | 2.9 |
| 0W-40， 5W-40， 10W-40 | - | - | 12.5 | 16.3 | 2.9 |
| 15W-40， 20W-40， 25W-40 | - | - | 12.5 | 16.3 | 3.7 |
| _W-50 | - | - | 16.3 | 21.9 | 3.7 |
| _W-60 | - | 21.9 | 26.1 | 3.7 |
Viscosity grade is that the engine oil of 0W has at-35 ℃ 6, the maximum cold-starting viscosity of 200cP, and at-40 ℃ 60, the maximum temperature pumping viscosity of the no yielding stress of 000cP and in the minimum low shear rate kinematic viscosity of 100 ℃ of 3.8cSt.Viscosity grade is that the engine oil of 5W has at-30 ℃ 6, the maximum cold-starting viscosity of 600cP, and at-35 ℃ 60, the maximum temperature pumping viscosity of the no yielding stress of 000cP and in the minimum low shear rate kinematic viscosity of 100 ℃ of 3.8cSt.Viscosity grade is that the engine oil of 10W has at-25 ℃ 7, the maximum cold-starting viscosity of 000cP, and at-30 ℃ 60, the maximum temperature pumping viscosity of the no yielding stress of 000cP and in the minimum low shear rate kinematic viscosity of 100 ℃ of 4.1cSt.Viscosity grade is that the engine oil of 15W has at-20 ℃ 7, the maximum cold-starting viscosity of 000cP, and at-25 ℃ 60, the maximum temperature pumping viscosity of the no yielding stress of 000cP and in the minimum low shear rate kinematic viscosity of 100 ℃ of 5.6cSt.
" spark-ignition internal combustion engine " is meant petrol engine.
" valve mechanism " in the oil engine is made up of valve and camshaft.At present, for the placement of valve and camshaft, two types the motor car engine that is designed for is arranged.If camshaft is positioned at the cylinder top, described engine is called as the overhead cam design; If camshaft is positioned on the engine body, described engine is called as the over-head valve design.The design of two classes all is installed in their valve above the cylinder at the cylinder top.This two classes design has been distinguished in the position of the camshaft of operated valve.Crest places the cam (DOHC) engine has two camshafts at each cylinder top; A camshaft operation suction valve, and another camshaft operations platoon air valve.
" low-sulfur diesel fuels " has the sulphur content of about 0.05Wt% at the most, measures by specified test among the ASTMD2622-87.
" low-sulphur oil " has the sulphur content that is lower than about 300ppm or 0.03%.
Except outstanding friction and abrasion resisting character, the lubricant base oil of blending of the present invention and the finished lubricants of blending have the character of hope, comprise high viscosity index, low Noack volatility, the oxidative stability of excellence and low pour point.Use resulting other benefit of described finished lubricants of the present invention to comprise wearing and tearing, longer oil change interval, waste oil that needs are still less disposed and the high temperature deposition thing of minimizing of minimizing of fuel economy, the engine parts of improvement.
The oxidative stability test:
Use two kinds of different testing method, promptly oxidizer BN measures oxidative stability with the oxidizer B with L-4 catalyzer.Oxidizer BN is used to measure the oxidative stability of the Fischer-tropsch derived lubricant base oil that does not contain any additives.A kind of method easily of measuring lubricant base oil stability is to use oxidizer BN test, as people such as Stangeland at United States Patent (USP) 3,852, described in 207.Oxidizer BN test is measured oxidation-resistance by the oxygen uptake device of Dornte type.Referring to R.W.Dornte, " oxidation of white oil ", " industry and engineering chemistry " rolled up the 26th page in 1936 the 28th.Usually, condition is the pure oxygen atmosphere at 340 .The result absorbs the required hours of 1000ml oxygen with 100g oil and reports.In oxidizer BN test, every 100g oil uses the 0.8ml catalyzer, and additive-package is included in the described oil.Catalyzer is the mixture of the soluble metal naphthenate in kerosene.The average metal analysis of the mixture simulation exhausted crankcase oils of described soluble metal naphthenate.The content of metal is as follows in the described catalyzer: copper=6,927ppm; Iron=4,083ppm; Plumbous=80,208ppm; Manganese=350ppm; Tin=3565ppm.Additive-package is the double focusing propylidene phenyl zinc dithiophosphate (zincbispolypropylenephenyldithio-phosphate) of oily 80 mmoles of per 100 grams, or the OLOA260 of about 1.1 grams.The response of described oxidizer BN thermometrically lubricant base oil in mimic is used.High value or the time that absorbs the required length of 1 liter of oxygen show good oxidative stability.Think that traditionally oxidizer BN should be higher than 7 hours.For the present invention, oxidizer BN value will be preferably greater than about 40 hours greater than about 30 hours.
Oxidizer B is used to measure the oxidative stability of the finished lubricants of the blending that has contained antioxidant addn.Oxidizer B test with L-4 catalyzer is the test (" industry and engineering chemistry " rolled up the 26th page in 1936 the 28th for R.W.Dornte, " oxidation of white oil ") of measuring oxidation-resistance by the oxygen uptake device of Dornte type.Usually, condition is the pure oxygen atmosphere at 340 , and the result absorbs the required hours of 1000ml oxygen with 100g oil and reports.In the oxidizer B test with L-4 catalyzer, every 100g oil uses the 0.8ml catalyzer.Catalyzer is the mixture of the soluble metal naphthenate in kerosene.The average metal analysis of the mixture simulation exhausted crankcase oils of described soluble metal naphthenate.The content of metal is as follows in the described catalyzer: copper=6,927ppm; Iron=4,083ppm; Plumbous=80,208ppm; Manganese=350ppm; Tin=3565ppm.Response with oxidizer B thermometrically finished lubricants in mimic is used of L-4 catalyzer.High value or the time that absorbs the required length of 1 liter of oxygen show good stability.Usually, the oxidizer B test result with L-4 catalyzer should be higher than about 7 hours.Preferably, having the value of the oxidizer B of L-4 will be greater than about 10 hour.The finished product concoction of blending of the present invention has much larger than 10 hours result.Preferably, the finished lubricants of blending of the present invention had greater than 22 hours, even more preferably greater than 30 hours the oxidizer B test result with L-4 catalyzer.
The HFRR wear testing:
Use high frequency reciprocating apparatus (HFRR) (PCS instrument HFR2) on the 1ml oil samples, to carry out wear testing, this high frequency reciprocating apparatus (HFRR) is in upset, overlapping and be polished to that (according to ANSI B3.12 grade is 24 less than the complete hardened ball that uses SAE-AISI E-52100 6.00mm diameter on the SAE-AISI E-52100 10mm square position of the polishing of 0.02 micron RA surface finish, Rockwell hardness " C " scale value that has 58-66 according to testing method ASTM E18, and has a surface finish) less than 0.05 micron RA, described square position has Vickers hardness " HV30 " according to standard E92, the Rockwell hardness of 190-210 " C " scale value.AISIE-52100 has the iron alloy that following typical element is formed: carbon, 1.00%; Manganese, 0.35%; Silicon, 0.25%; And chromium, 1.50%.Test condition is as follows: frequency 20Hz; The load 1 that applies, 000g; Length of stroke 1mm; 120 ℃ of fluid temperature (F.T.)s, relative humidity is greater than 30% and test time 200 minutes.Described test is the revision of the test described in ASTM D6079.
Because the extreme difference of hardness between ball and the dish, most of fret wears occur on the dish, are the form of the long hemispherical wear print of 1mm.Therefore, wear resistance is only based on the amount from the material that removes of dish, and not based on the amount of the material that removes from ball.At first remove thin wear debris from the surface of coiling with the cotton swab that is soaked with hexane, then near wear print with the profile of the rectangular area of the 1/24mm * 1.64mm on MicroXAM-100 3D Surface Profiler (ADE phase shift) the described surface of drawing, carry out mill afterwards and decrease cubing.At first use the software program of making even of MicroXAM the surface profile of described dish to be made even based on the flat site of the described wear print of next-door neighbour, then from deducting the metal volume (wearing and tearing) more than the plane of giving prominence at the void volume that extends under the plane on surface (adhesion), calculate the difference between material volume (wearing and tearing (lubricant releasedwear) that lubricant discharges) that removes by bounding force and the material volume that passes through wearing and tearing (plough) transfer on the surface.Come from the HFRR of the void volume that extends under the plane on surface wear volume and the clean wear print volume of HFRR and be reported as wear volume and the clean wear volume of HFRR under the HFRR plane respectively, unit is a cu.Volume accuracy by this commercial measurement is ± 10 cus according to estimates.All lubricant tests twice, and with results averaged.
Preferably, finished lubricants of the present invention has shown 1, under the load that 000g applies less than 300, wear volume under the HFRR plane of 000 cu is more preferably less than or equals wear volume under the HFRR plane of about 170,000 cus, even be more preferably less than 150, wear volume and even be more preferably less than wear volume under the HFRR plane of 110,000 cus under the HFRR plane of 000 cu.In addition, finished lubricants of the present invention has shown the clean wear volume less than the HFRR of 100,000 cus, preferably less than the clean wear volume of the HFRR of 50,000 cus be more preferably less than the clean wear volume of HFRR of 25,000 cus.
Other lubricant test:
Kinematic viscosity is measuring of the resistance of fluid when the action of gravity current downflow.Employed fluidic proper viscosity is depended in many lubricant base oils, the finished lubricants of being made by lubricant base oil and the correct operation of equipment.Measure kinematic viscosity by ASTM D 445-01.The result reports with centistoke (unit of kinematic viscosity) Si (cSt).The finished lubricants of blending of the present invention is 100 ℃ of kinematic viscosity with the about 20cSt of about 2.0cSt-.
Viscosity index (VI) is a numeral empirical, no unit, and the expression temperature variation is to the influence of the kinematic viscosity of oil.Liquid viscosity is with temperature change, and viscosity reduces when being heated; The VI of oil is high more, and the trend that its viscosity with temperature changes is low more.Relative constant viscosity is arranged in any case in wide region, need the lubricant of high VI under the temperature that requires to change.Can described in ASTM D2270-93, measure VI.Preferably, the finished lubricants of blending of the present invention has the viscosity index greater than 140, the viscosity index more preferably greater than 165.
Measuring of the temperature of pour point when to be the lubricant base oil sample begin to flow under the condition of careful control.Can described in ASTM D5950-02, measure pour point.The result is with a degree centigrade report.Many commercial lubricant base oils have technical requirements to pour point.When lubricant base oil had low pour point, they also had other good cryogenic properties probably, for example low cloud point, low cold filter stoppage point and cold-starting viscosity.Cloud point is that the complementarity of pour point is measured, and the temperature when being expressed as the lubricant base oil sample and beginning muddiness to occur under careful defined terms.Can measure cloud point by for example ASTM D5773-95.
According to ASTM D5800, the Noack volatility be defined as when oil in being connected with the test crucible of constant air flow at 250 ℃ with than the low 20mmHg (2.67kPa of normal pressure; 26.7mbar) the following quality of the oil that lost in 60 minutes of heating of pressure, represent with wt%.Calculate the method more easily of Noack volatility and be to use thermogravimetric analyzer test (TGA) according to ASTM D6375 with the closely-related method of ASTM D5800.Unless stated otherwise, in whole specification sheets disclosure, use TGA Noack volatility.Find, relevant with the oil consumption of bus engine by TGA Noack with the Noack volatility of the engine oil of similar approach mensuration.To the strict demand of low volatility is the important aspect of several nearest CCMC engine oil specifications (for example ILSAC GF-3 of Ou Zhou ACEA A-3 and B-3 and North America).Preferably, the finished lubricants of blending of the present invention has the Noack volatility less than 12wt%.
Cold cranking simulator apparent viscosity (CCS VIS) is the test that is used for measuring the viscometric properties of lubricant base oil under low temperature and high-shear.CCS VIS also can be called as cold-starting viscosity.The testing method of determining CCS VIS is ASTM D5293-02, carries out under the design temperature between-5 ℃ and-35 ℃.The result is with centipoise (cP) report.Found that CCS VIS is relevant with the cryogenic engine starting.The SAE J300 of revision in June calendar year 2001 has defined the specification of maximum CCS VIS at automobile engine oil.
The condition of high temperature high shearing viscosity (HTHS) tolerance fluid high-load shaft bearing in being similar to the oil engine of igniting (typically 100 ten thousand seconds
-1, at 150 ℃) under resistance to flow.Compare with 100 ℃ low shear rate kinematic viscosity, HTHS shows to adopt given lubricant oil engine how at high temperature to move better.HTHS is directly related with the oil film thickness in the bearing.The SAE J300 in June, 01 contains the existing standard of the HTHS that measures by ASTM D4683, ASTM D4741 or ASTMD5481.
Mini rotary viscosity (MRV) but relate to the mechanism of pumping, and be the measurement of low shear rate.MRV measures by ASTM D4684, and also can be called as temperature pumping viscosity.The sample rate of cooling is the key feature of this method slowly.Pretreatment sample makes it have specified thermal history, comprises heating, slowly cooling off and Xu's thermal cycling.MRV measures apparent yielding stress, if it is greater than threshold value, will show potential air sinuses pumping failure problem.Specific viscosity (at present the SAE J300 by June calendar year 2001 is defined as 60,000cP) more than, oil may be failed by pumping by the mechanism that is called as " flow limitation " behavior.For example, require SAE 10W oil to have 60 at-30 ℃, the maximum of 000cP does not have yielding stress viscosity.This method is also measured at 1-50s
-1Shearing rate under apparent viscosity.
TEOST MHT is the test that the thermooxidizing engine oil simulation test (TEOST) of utilization under medium hot conditions measured the sedimental amount (is unit with the milligram) that is formed by automobile engine oil.Design described testing method, form trend with the high temperature deposition thing of predicting engine oil under the temperature of being found in the ring belt zone (about 300 ℃).TEOST MHT can carry out on this area has been used for the TEOST 33C bench testing unit of ASTM D6335, adopts the test condition of improved hardware and modification.Main hardware differences is: the glass deposition device bar cover that 1) replaces steel, allow to observe oxidation/deposition process, 2) the depositor bar of wire-wound flows through the bar and 3 of heating to allow oily film like) in test process, put the collection of the evaporable material of generation at the depositor bar.Be used for the up-to-date engine oil service category of automotive gasoline engine, TEOST MHT has the total sedimental maximum specification of 45mg.The API SL/ILSAC GF-3 oil expection that provides the high temperature deposition thing control performance of improvement in this test will provide persistent oil extraction ability, lower abradability wearing and tearing, the piston ring spatter property that improves, longer engine life and the turbocharger performance of improvement.Turbo-supercharger is exhaust-driven pump, and its compression inhaled air also promotes it and enters the combustion chamber being higher than under the atmospheric pressure.The air pressure that increases allows more fuel combustion and causes producing bigger horsepower.Table II has been summarized TEOST MHT rules.
Table II: TEOST MHT rules
| Test duration | 24 hours |
| Temperature | 285℃ |
| Sample size | 10mL |
| Flow rate (sample) | 0.25g/min |
| Flow rate (dry air) | 12mL/min |
| Catalyzer | Fe+Pb+Sn |
The finished lubricants of blending of the present invention preferably has the total settling weight of the TEOST-MHT that is less than or equal to about 45mg.
Fischer-Tropsch is synthetic
Pass through Fischer-tropsch process, then carry out the hydroisomerization of the waxy fraction of Fischer-Tropsch synthetic crude, prepare described comprising 〉=6wt% have that mononaphthene belongs to the molecule of functionality and less than the Fischer-tropsch derived lubricant base oil of the molecule of 0.05wt% with aromatic functionality.
In the Fischer-Tropsch chemistry, synthetic gas changes into liquid hydrocarbon by contacting with fischer-tropsch catalysts under reaction conditions.Typically, methane and optional heavier hydrocarbon (ethane and heavier hydrocarbon) can be sent to traditional synthetic gas generator, so that synthetic gas to be provided.Usually, synthetic gas contains hydrogen and carbon monoxide, and may comprise a spot of carbonic acid gas and/or water.Do not wish to exist in the synthetic gas sulphur, nitrogen, halogen, selenium, phosphorus and arsenic contamination thing.For this reason and depend on the quality of synthetic gas, preferably before implementing the Fischer-Tropsch chemistry, from raw material, remove desulfuration and other pollutent.The means of removing these pollutents are well-known to those skilled in the art.For example, for removing sulphur impurity, ZnO protection bed is preferred.The means of removing other pollutent are well-known to those skilled in the art.May also wish before fischer-tropsch reactor, to purify described synthetic gas, with any other sulphur compound of removing the carbonic acid gas that in the synthesis gas reaction process, produces and not removing.For example, this can contact and realize with the solution (for example wet chemical) that omits slight alkalinity in packing tower by making synthetic gas.
In Fischer-tropsch process, comprise H
2Under suitable temperature and pressure reaction conditions, contact with fischer-tropsch catalysts with the synthetic gas of the mixture of CO, generate the liquids and gases hydrocarbon.Fischer-tropsch reaction generally carries out under the following conditions: about 300-700 (149-371 ℃), the temperature of preferably about 400-550 (204-228 ℃); About 10-600psia (0.7-41 crust), the pressure of preferably about 30-300psia (2-2 1 crust); With about 100-10,000cc/g/hr, preferably about 300-3, the catalyzer air speed of 000cc/g/hr.The example that carries out the condition of fischer-tropsch type reaction is well-known to those skilled in the art.
The product of Fischer-Tropsch synthesis method can be at C
1-C
200+In the scope, most of at C
5-C
100+In the scope.Described reaction can be carried out in various types of reactors, for example contains the combination of fixed-bed reactor, slurry-phase reactor, fluidized-bed reactor or various types of reactors of one or more beds.These reaction process and reactor are known and on the books in the literature.
Slurry Fischer-tropsch process (it is preferred in enforcement of the present invention) has utilized heat (and quality) transmission characteristic of the excellence that is used for strong exothermic reaction, and can produce relative high-molecular weight paraffinic hydrocarbons when using cobalt catalyst.In described slurry process, the synthetic gas of mixture that comprises hydrogen and carbon monoxide as the third phase bubbling by comprising the slurry of particulate state fischer-tropsch hydrocarbon synthesis catalyst, described catalyzer disperses and is suspended in the slurry liquid, and it is the hydrocarbon product of the described building-up reactions of liquid that this slurry liquid is included under the reaction conditions.The mol ratio of hydrogen and carbon monoxide can be broadly in the scope of about 0.5-about 4, but more typically in the scope of about 0.7-about 2.75, and preferred in the scope of about 0.7-about 2.5.Instructed a particularly preferred Fischer-tropsch process in EP0609079, the document also all is attached to herein by reference for all purposes.
Usually, fischer-tropsch catalysts contains the group VIII transition metal on metal oxide carrier.Described catalyzer can also contain noble metal promoted agent and/or crystalline molecular sieve.Suitable fischer-tropsch catalysts comprises one or more among Fe, Ni, Co, Ru and the Re, and wherein cobalt is preferred.A kind of preferred fischer-tropsch catalysts is included in suitable inorganic carrier material, preferably comprises the cobalt of the significant quantity on the inorganic carrier material of one or more refractory metal oxides and among Re, Ru, Pt, Fe, Ni, Th, Zr, Hf, U, Mg and the La one or more.Usually, be present in the amount of the cobalt in the described catalyzer between about 1 and about 50wt% of total catalyst composition.Described catalyzer can also contain basic oxide promotor such as ThO
2, La
2O
3, MgO and TiO
2, promotor such as ZrO
2, precious metal (Pt, Pd, Ru, Rh, Os, Ir), coinage metal (Cu, Ag, Au) and other transition metal such as Fe, Mn, Ni and Re.The suitable carriers material comprises aluminum oxide, silicon-dioxide, magnesium oxide and titanium dioxide, or their mixture.For the catalyzer that contains cobalt, preferred carrier comprises titanium dioxide.United States Patent (USP) 4,568, open and illustrated useful catalysts and their preparation method in 663, this is illustrating rather than limiting about what catalyzer was selected.
It is low relatively to moderate chainpropagation probability that known some catalyzer provides, and reaction product comprises a high proportion of relatively lower molecular weight (C
2-8) alkene and the relative high molecular (C that hangs down ratio
30+) wax.Known some other catalyzer provides high relatively chainpropagation probability, and reaction product comprises the lower molecular weight (C of low relatively ratio
2-8) alkene and relative a high proportion of high molecular (C
30+) wax.Such catalyzer is well known to a person skilled in the art, and can easily obtain and/or prepare.
Product from Fischer-tropsch process mainly contains paraffinic hydrocarbons.Product from fischer-tropsch reaction generally comprises light reaction product and wax reaction product.Described light reaction product (being the condensation product cut) is included in the following ebullient hydrocarbon of about 700 (for example tail gas-diesel oil fuel), and is most of at C
5-C
20In the scope, contain the hydrocarbon of the bigger carbon number of reduction gradually, be up to about C
30Described wax reaction product (being wax slop) is included in the above ebullient hydrocarbon of about 600 (for example vacuum gas oil-heavy paraffin), and is most of at C
20+In the scope, contain the hydrocarbon of the littler carbon number of reduction gradually, minimum to C
10Described light reaction product and described waxy product are that alkane belongs to basically.Described waxy product comprises the normal paraffin greater than 70wt% usually, often comprises the normal paraffin greater than 80wt%.Described light reaction product comprises alkane and belongs to product, has the pure and mild alkene of remarkable ratio.In some cases, described light reaction product can comprise nearly 50wt% or even higher pure and mild alkene.Described wax reaction product (being described wax slop) is used as the raw material of the method for the lubricant base oil that provides Fischer-tropsch derived, and described Fischer-tropsch derived lubricant base oil is used for the lubricant of blending of the present invention and the finished lubricants of blending.
By comprising the technology of hydroisomerization, from the waxy fraction preparation of described Fischer-Tropsch synthetic crude comprise 〉=6wt% have that mononaphthene belongs to the molecule of functionality and less than the Fischer-tropsch derived lubricant base oil of the molecule of 0.05wt% with aromatic functionality.Preferably, by the U.S.S.N.10/744 that submits on December 23rd, 2003, the U.S.S.N.10/744 that on December 23rd, 389 and 2003 submitted to, the technology described in 870 prepares described Fischer-tropsch derived lubricant base oil, by reference described document integral body is attached to herein.The described Fischer-tropsch derived lubricant base oil that is used for the finished lubricants of the lubricant of blending of the present invention and blending can be made in different place, the place that is received and concocts with the component of the lubricant of described blending.
Hydroisomerization
The hydroisomerization intention adds the cold flow character that branching is improved lubricant base oil by selectivity in molecular structure.Hydroisomerization will be realized the high level of conversion of Fischer-Tropsch wax to non-wax isoparaffin ideally, make simultaneously by the cracked conversion to minimize.Preferably, in the present invention control the condition of hydroisomerization, the conversion of compounds rate that compound to the boiling point that makes the wax stock mid-boiling point be higher than about 700 is lower than about 700 maintains between about 10wt% and the 50wt%, preferably between 15wt% and 45wt%.
According to the present invention, use is selected the shape mesoporous molecular sieve and is carried out hydroisomerization.Be used for hydroisomerisation catalysts of the present invention and comprise and select the shape mesoporous molecular sieve, and randomly be included in the metal hydrogenation component of the catalytic activity on the refractory oxide carrier.Wording used herein " mesopore " is meant the effective pore radius in the about 7.1 dust scopes of about 3.9-when described porous inorganic oxide is burnt form.Described shape mesoporous molecular sieve normally 1-D10-, 11-or the 12-toroidal molecule sieve selected that in enforcement of the present invention, uses.Preferred molecular sieve of the present invention is a 1-D10-ring variant, and wherein 10-(or 11-or 12-) toroidal molecule sieve has the atom (T-atom) of the individual tetrahedral coordination that connects by oxygen in 10 (or 11 or 12).In the 1-D molecular sieve, described 10-ring (or bigger) hole is parallel to each other, and does not interconnect.Yet, note, satisfy the described broad definition of mesoporous molecular sieve but comprise the 1-D10-toroidal molecule sieve in the hole with 8 yuan of rings of intersection, also can covered in the definition of described molecular sieve of the present invention.At R.M.Barrer, Zeolites, Science and Technology, edited byF.R.Rodrigues, L.D.Rollman and C.Naccache, NATO ASI Series has illustrated the classification (1-D, 2-D and 3-D) of zeolite inner duct in 1984, and this classification all is attached to herein (seeing 75 pages especially) by reference.
What be used for hydroisomerization preferably selects the shape mesoporous molecular sieve based on aluminum phosphate, for example SAPO-11, SAPO-31 and SAPO-41.SAPO-11 and SAPO-31 are preferred, and SAPO-11 is most preferred.SM-3 is the particularly preferred shape mesopore SAPO that selects, and its crystalline structure drops in the crystalline structure scope of SAPO-11 molecular sieve.At United States Patent (USP) 4,943, the preparation of SM-3 and the feature of its uniqueness have been described in 424 and 5,158,665.The shape mesoporous molecular sieve of equally preferably selecting that is used for hydroisomerization is a zeolite, for example ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, SSZ-32, offretite and ferrierite.SSZ-32 and ZSM-23 are preferred.
Preferred mesoporous molecular sieve is characterised in that the free diameter of crystallography in the duct of selection, grain-size of selection (corresponding to the orifice throat length of selecting) and the acidity of selecting.The free diameter of the crystallography of the hope of molecular sieve pore passage is in the scope of about 7.1 dusts of about 3.9-, and the maximum free diameter of crystallography is not more than 7.1 dusts and the minimum free diameter of crystallography is not less than 3.9 dusts.Preferably, the maximum free diameter of crystallography is not more than 7.1 dusts, and the minimum free diameter of crystallography is not less than 4.0 dusts.Most preferably, the maximum free diameter of crystallography is not more than 6.5 dusts, and the minimum free diameter of crystallography is not less than 4.0 dusts.At " Atlas of Zeolite FrameworkTypes ", Fifth Revised Edition, 2001, by Ch.Baerlocher, W.M.Meier, and D.H.Olson, Elsevier, disclose the free diameter of crystallography of molecular sieve pore passage among the pp10-15, the document is combined in herein by reference.
A kind of particularly preferred mesoporous molecular sieve that can be used for the inventive method for example is described in the United States Patent (USP) 5,135,638 and 5,282,958, and the content of described document integral body by reference is combined in herein.At United States Patent (USP) 5,282, in 958, a kind of like this mesoporous molecular sieve has and is not more than about 0.5 micron grain-size and the minimum diameter hole at least about 4.8 dusts and about 7.1 dusts of maximum diameter.Described catalyzer has enough acidity, so that in being placed on tubular reactor the time, under the feed rate of 370 ℃, the hydrogen flow of the pressure of 1200psig, 160ml/min and 1ml/hr, the described catalyzer of 0.5g transforms at least 50% n-Hexadecane.When at the n-hexadecane (n-C that causes 96%
16) when to the condition of the transformation efficiency of other species, using, described catalyzer also show 40% or bigger isomerization selectivity (the isomerization selectivity is following to be determined: 100 * (branching C in the product
16Wt%)/(branching C in the product
16The wt%+ product in C
13-wt%)).
If the free diameter of the crystallography of molecular sieve pore passage is unknown, can use standard adsorption technology and the known hydrocarbon materialization of minimum power diameter compound to measure effective hole size of molecular sieve.Referring to Breck, Zeolite Molecular Sieves, 1974 (particularly the 8th chapters); Anderson et al.J.Catalysis 58,114 (1979); With United States Patent (USP) 4,440,871, the relevant portion of described document is combined in herein by reference.In adsorbing the process of measurement, use standard techniques with definite hole size.If a kind of specific molecule in less than about 10 minutes time, do not reach its equilibrium adsorption value on molecular sieve at least 95% (at 25 ℃, p/p
0=0.5), thinks that it is suitable that this specific molecule is left out.It is the molecule of 5.3-6.5 dust and obstruction is seldom arranged that mesoporous molecular sieve generally can be admitted kinetic diameter.
Can be used for the hydrogenation metal that hydroisomerisation catalysts of the present invention comprises catalytic activity.The existence of the hydrogenation metal of described catalytic activity has caused the improvement of product, particularly VI and stability.The hydrogenation metal of typical catalytic activity comprises chromium, molybdenum, nickel, vanadium, cobalt, tungsten, zinc, platinum and palladium.Metal platinum and palladium are particularly preferred, and platinum is most preferred.If use platinum and/or palladium, the total amount of active hydrogenation metal usually in the scope of 0.1-2wt%, and is no more than 10wt% generally in the scope of the 0.1-5wt% of total catalyst.
Refractory oxide carrier can be selected from those oxide carriers that are generally used for catalyzer, comprises silicon-dioxide, aluminum oxide, silica-alumina, magnesium oxide, titanium dioxide and their combination.
Regulate the condition of hydroisomerization, with comprised 〉=6wt% have that mononaphthene belongs to the molecule of functionality and less than the Fischer-tropsch derived lubricant base oil of the molecule of 0.05wt% with aromatic functionality.The condition of hydroisomerization will depend on whether employed raw material properties, employed catalyzer, described catalyzer cure, the character of desirable yield and desirable lubricant base oil.
The condition that can carry out hydroisomerisation process of the present invention comprises: about 600 -Yue 750 (315 ℃-Yue 399 ℃), the temperature of preferred about 600 -Yue 700 (315 ℃-Yue 371 ℃); With about 15-3000psig, the pressure of preferred 100-2500psig.In context, hydroisomerization dewaxing pressure is meant the hydrogen dividing potential drop in hydroisomerization reactor, although this hydrogen dividing potential drop identical with stagnation pressure basically (or much at one).In contact process, liquid hourly space velocity is generally about 0.1-20hr
-1, the about 5hr of preferably about 0.1-
-1The ratio of hydrogen and hydrocarbon is at the about 50 moles of H of about 1.0-
2In the scope of/mole hydrocarbon, more preferably in the scope of the about 20 moles of H2/ mole hydrocarbon of about 10-.At United States Patent (USP) 5,282, the conditions suitable that carries out hydroisomerization has been described in 958 and 5,135,638, the content of described patent all is attached to herein by reference.
In the process of hydroisomerisation process, hydrogen is present in reaction zone ,-as be about 0.5-30MSCF/bbl (MSCF (Thousand standard cubic feet)/bucket) with the ratio of hydrogen and raw material, the amount of the about 10MSCF/bbl of preferably about 1-exists.Hydrogen can be separated with product, and hydrogen is recycled to reaction zone.
Hydrotreatment
Before the hydroisomerization dewaxing, the waxy feed of hydroisomerisation process can be by hydrotreatment.Hydrotreatment is meant a kind of catalytic process of carrying out usually in the presence of free hydrogen, wherein main purpose is to remove various metal pollutants, for example arsenic, aluminium and cobalt; Heteroatoms, for example sulphur and nitrogen; Oxygenate; Or from the aromatic substance of raw material.Usually, in the hydrotreatment operation, the cracking of hydrocarbon molecule (promptly bigger hydrocarbon molecule fragments into less hydrocarbon molecule) is minimized, and unsaturated hydrocarbons is by complete hydrogenation or partial hydrogenation.
The catalyzer that is used to carry out the hydrotreatment operation is known in the art.About the general description of hydrotreatment, hydrocracking and the typical catalyst used in each of this two processes, referring to for example United States Patent (USP) 4,347,121 and 4,810,357, its content all is attached to herein by reference.Appropriate catalyst comprises the precious metal from VIII A family 1975 rules of applied chemistry federation (pure according to the world and), for example at aluminum oxide or contain platinum or palladium on the silicon matrix, with metal, for example at aluminum oxide or contain nickel-molybdenum or nickel-Xi on the silicon matrix from group VIII and group vib.United States Patent (USP) 3,852,207 have described suitable noble metal catalyst and gentle condition.Other appropriate catalyst for example is described in the United States Patent (USP) 4,157,294 and 3,904,513.Non-your hydrogenation metal, nickel-molybdenum for example, generally the form with oxide compound is present in the final catalyst composition, but generally is used with its reductive or sulfurized form, when such sulfide easily when related special metal forms.Preferred non-noble metal catalyst compositions contains and surpasses about 5wt%, the molybdenum of the about 40wt% of preferably about 5-and/or tungsten and at least about 0.5wt%, and nickel and/or the cobalt of the about 15wt% of generally about 1-, described amount is in corresponding oxide compound.The catalyzer that contains precious metal such as platinum contains and surpasses 0.01% metal, the metal of preferred 0.1-1.0%.Also can use the combination of precious metal, for example the mixture of platinum and palladium.
The condition of typical hydrotreatment changes in wide region.Usually, total LHSV is about 0.25-2.0, preferably about 0.5-1.5.The hydrogen dividing potential drop is greater than 200psia, preferably in the scope of the about 2000psia of about 500psia-.The hydrogen recirculation rate is generally greater than 50SCF/Bbl, preferably 1000 and 5000SCF/Bbl between.Temperature in the reactor is in the scope of about 300 -Yue 750 (about 150 ℃-Yue 400 ℃), preferably in the scope of 450 -725 (230 ℃-385 ℃).
Hydrofining
Hydrofining is a kind of hydroprocessing process, and it can be used as the hydroisomerization step afterwards of the lubricant base oil that provides Fischer-tropsch derived.The hydrofining intention is improved oxidative stability, UV stability and the outward appearance of Fischer-tropsch derived lubricant base oil products by aromatic substance, alkene, chromoplastid and the solvent of removing trace.The term of Shi Yonging " UV stability " is meant the stability when lubricant base oil or finished lubricants are exposed to UV light and oxygen in this manual.When the visible throw out forms (usually as floss or muddy and seen) or darker color and occurs after being exposed to UV-light and air, illustrate to have unstable.At United States Patent (USP) 3,852, can find hydrorefined general description in 207 and 4,673,487.
Can hydrofining Fischer-tropsch derived lubricant base oil of the present invention, to improve product quality and stability.In unifining process, total liquid hourly space velocity (LHSV) is about 0.25-2.0hr
-1, preferably about 0.5-1.0hr
-1The hydrogen dividing potential drop is greater than 200psia, preferably in the scope of the about 2000psia of about 500psia-.The hydrogen recirculation rate is generally greater than 50SCF/Bbl, preferably 1000 and 5000SCF/Bbl between.Temperature is in the scope of about 300 -Yue 750 , preferably in the scope of 450 -600 .
Suitable Hydrobon catalyst comprises the precious metal from VIIIA family 1975 rules of applied chemistry federation (pure according to the world and), for example at aluminum oxide or contain platinum or palladium on the silicon matrix, with unvulcanized VIIIA family and group vib metal, for example at aluminum oxide or contain nickel-molybdenum or nickel-Xi on the silicon matrix.United States Patent (USP) 3,852,207 have described suitable noble metal catalyst and gentle condition.Other appropriate catalyst for example is described in the United States Patent (USP) 4,157,294 and 3,904,513.Base metal such as nickel-molybdenum and/or tungsten and at least about 0.5wt%, nickel and/or the cobalt of the about 15wt% of generally about 1-are in corresponding oxide compound.Precious metal (for example platinum) catalyzer contains and surpasses 0.01% metal, the metal of preferred 0.1-1.0%.Also can use the combination of precious metal, for example the mixture of platinum and palladium.
Clay treatment is to remove the alternative final processing step that impurity provides Fischer-tropsch derived lubricant base oil.
Fractionation
Randomly, the described method that Fischer-tropsch derived lubricant base oil is provided can be included in the wax stock that the described alkane basically of fractionation belongs to before the hydroisomerization, or fractionation derives from the lubricant base oil of hydroisomerisation process.Generally Fischer-Tropsch wax raw material or the lubricant base oil that described alkane basically belongs to is fractionated into the overhead product cut by air distillation or vacuum distilling or the combination by air distillation and vacuum distilling.The tower bottom distillate that air distillation generally is used for lighter overhead product cut (for example petroleum naphtha and diesel oil) and initial boiling point are higher than about 600 -Yue 750 (about 315 ℃-Yue 399 ℃) separates.Under higher temperature, the thermo-cracking of hydrocarbon may take place, cause equipment scaling and cause lower last running yield.Vacuum distilling generally is used to the material of higher such as lubricant base oil cut are separated into the cut of different boiling ranges.The cut that lubricant base oil is fractionated into different boiling ranges makes the factory that makes lubricant base oil can produce the lubricant base oil more than a grade or viscosity.
Solvent dewaxing
The method for preparing Fischer-tropsch derived lubricant base oil can also comprise the step of solvent dewaxing after hydroisomerisation process.Solvent dewaxing randomly can be used to remove a spot of remaining waxy molecules from hydroisomerization dewaxing lubricant base oil afterwards.By being dissolved in solvent such as methylethylketone, methyl iso-butyl ketone (MIBK) or the toluene, lubricant base oil carries out solvent dewaxing, perhaps, the wax molecule carries out solvent dewaxing by being precipitated, as Chemical Technology ofPetroleum, 3rd Edition, William Gruse and Donald Stevens, McGraw-Hill Book Company, Inc., New York, 1960, discussed among the pages 566-570.United States Patent (USP) 4,477 has also been described solvent dewaxing in 333,3,773,650 and 3,775,288.
Fischer-tropsch derived lubricant base oil
Be used to prepare the lubricant of blending of the present invention and blending finished lubricants Fischer-tropsch derived lubricant base oil 100 ℃ preferably have about 2 and 20cSt between viscosity.
Described Fischer-tropsch derived lubricant base oil comprises 〉=6wt% have a molecule that mononaphthene belongs to functionality, preferred 〉=8wt% has a molecule that mononaphthene belongs to functionality, even more preferably 〉=10wt% have a molecule that mononaphthene belongs to functionality.In a preferred embodiment, described Fischer-tropsch derived lubricant base oil comprises the very aromatic substance of low weight percentage, high weight percent have cycloalkanes belong to functionality molecule and high have mononaphthene belong to functionality molecule weight percent with have polynaphthene belong to functionality molecule weight percent ratio (or high weight percent have mononaphthene belong to the molecule of functionality and very low weight percentage have a molecule that polynaphthene belongs to functionality).Described Fischer-tropsch derived lubricant base oil comprises less than 0.05wt%, preferably less than the molecule with aromatic functionality of 0.02wt%.In a preferred embodiment, described Fischer-tropsch derived lubricant base oil comprises the molecule that cycloalkanes belongs to functionality that has greater than 10wt%, with high have mononaphthene belong to functionality molecule weight percent with have polynaphthene and belong to the ratio of weight percent of the molecule of functionality, be preferably greater than 15 have mononaphthene belong to functionality molecule weight percent with have polynaphthene and belong to the ratio of weight percent of the molecule of functionality.In still another preferred embodiment, described Fischer-tropsch derived lubricant base oil comprises the molecule with aromatic functionality less than 0.05wt%, greater than 10wt% have that mononaphthene belongs to the molecule of functionality and less than the molecule that polynaphthene belongs to functionality that has of 0.1wt%.
The described Fischer-tropsch derived lubricant base oil of the lubricant that is used for concocting and the finished lubricants of blending contains the saturates greater than 95wt%, measures by wash-out column chromatography ASTM D2549-02.The amount of alkene is lower than the C by long duration (long duration)
13The detectable amount of nuclear magnetic resonance spectrum (NMR).Amount with molecule of aromatic functionality is lower than 0.05wt%, measures by HPLC-UV, and confirms by the ASTM D5292-99 that is modified to measure the low levels aromatic substance.In preferred embodiments, the amount with molecule of aromatic functionality is lower than 0.02wt%, preferably is lower than 0.01wt%.
The amount of sulphur is more preferably less than 1ppm less than 25ppm, measures with ultraviolet fluorescence method according to ASTM D5453-00.
Measure by the aromatic substance that HPLC-UV carries out
Be used for measuring method at the molecule with aromatic functionality of the low levels of Fischer-tropsch derived lubricant base oil, use 1050 serial four gradient high performance liquid chromatography (HPLC) systems of Hewlett-Packard, this system is furnished with the HP1050 diode array UV-Vis detector that is connected with the HP chem workstation by the interface.Based on their UV spectrum pattern and their elution time, identify each aromatic substances in HI SA highly saturated Fischer-tropsch derived lubricant base oil.The nh 2 column that is used for this analysis is mainly distinguished aromatic molecules based on the number of rings of aromatic molecules (or more precisely, double key number).Like this, the aromatic molecules that contains single ring will be at first by wash-out, is the polycyclic aromatic substance then by the cumulative double key number purpose order of per molecule by wash-out.For the aromatic substance with similar two key features, those that only have on the ring that alkyl replaces will be than those wash-outs quickly with cycloalkyl substituted.
The peak transition of electron of various base oil aromatic hydrocarbons is with respect to the whole red shifts of pure model compound analogue (being somewhat dependent upon the alkyl on the member ring systems and the amount of cycloalkyl substituted), and this true making identifies clearly that from the UV absorption spectrum of various base oil aromatic hydrocarbons they are somewhat complicated.These red shifts are that the alkyl delocalization by the π-electronics on the aromatic ring causes as everyone knows.Owing to seldom have unsubstituted aromatic substance to seethe with excitement in the lubricant scope, red shift to a certain degree is among expecting, and all observes to a certain degree red shift for certified all main aromatic groups.
By on the appropriate retention time window of the aromatic substance of wash-out to the color atlas integration finish this aromatic substance quantitatively, described color atlas is made by the wavelength at each big class optimization of compound.Similarity on qualitative is assigned to appropriate aromatic substance class with them at each absorption spectrum of the compound of different time wash-out and based on them and model compound absorption spectrum by artificial evaluation, determines the retention time window limits for each aromatic substance class.Exception is seldom arranged, in HI SA highly saturated API II group and III group lubricant base oil, only observe 5 class aromatic substance.
The HPLC-UV calibration
HPLC-UV is used to identify even the unusual aromatic substance of these classes of low levels.The absorption of polynuclear aromatic compound generally than the strong 10-200 of the absorption of monocyclic aromatics doubly.Alkyl replaces also, and influence absorbs about 20%.Therefore, use HPLC separates and identifies various aromatic substance and know that how they absorb effectively is important.
5 class aromatic substance have been identified.Between the alkylnaphthalene class of the alkyl-1-cyclophane family's naphthenic hydrocarbon that keeps at topnotch and least highly reservation, have little overlapping, all aromatic substance kinds are baseline separation.Determine for the 1-ring of described co-elute and the integration boundaries of 2-cyclophane compounds of group at 272nm by vertical line dropping method (perpendicular dropmethod).By setting up Beer law figure,, at first determine the response factor that depends on wavelength of the big class of each aromatic substance based on the spectrum peak absorbancy the most close with the aromatics analogue of described replacement from pure model compound mixture.
For example, the alkyl in the base oil-phenylcyclohexane molecule demonstrates clearly peak value absorbancy at 272nm, identical (taboo) transition that this takes place at the 268nm place corresponding to unsubstituted 1,2,3,4-tetralin model compound.By supposing that alkyl-1-cyclophane family naphthenic hydrocarbon is at the molar absorptivity response factor at 272nm place and from 1 of Beer law figure calculating, 2,3, the 4-tetraline calculates the concentration of alkyl-1-cyclophane family naphthenic hydrocarbon in the base oil sample in the molar absorptivity approximately equal at 268nm place.Be approximately equal to the molecular-weight average of whole base oil sample by the molecular-weight average of supposing each aromatic substance class, calculate the weight percent concentration of aromatic substance.
By directly from lubricant base oil, separating described 1-cyclophane compounds of group, further improve described calibration steps via HPLC chromatogram completely.Directly calibrate and eliminated hypothesis and the uncertainty that is associated with model compound with these aromatic substance.As expected, isolating aromatic substance sample has the response factor lower than model compound, because it is more highly to replace.
More specifically, in order accurately to calibrate described HPLC-UV method, use Waters partly to prepare the HPLC device is isolated replacement from described lubricant base oil body benzene aromatic substance.With the dilution in 1: 1 in normal hexane of 10g sample; and be expelled to the silica column (guard column of 5cm * 22.4mm ID) of amino bonded; 25cm * 22.4mm ID the post of the silica dioxide granule of the amino bonded by two 8-12 microns is (by Rainin Instruments then; Emeryville; California makes), adopting flow is that the normal hexane of 18ml/min is as moving phase.Based on detector response, with the classification of post eluant from the dual wavelength UV detector that is set in 265nm and 295nm.Collect the saturates fraction and show the variation of 0.01 absorbance unit up to the 265nm absorbancy, this is the signal that the wash-out of monocyclic aromatics begins.Collect the absorbancy ratio of monocyclic aromatics fraction up between 265nm and 295nm and drop to 2.0, this wash-out that shows bicyclic-aromatic compound begins.By " hangover " saturates fraction of described single aromatic substance fraction being carried out chromatogram again, isolate causing owing to the HPLC column overload, the purifying that carries out described monocyclic aromatics fraction with separate.
The aromatics of described purifying " standard substance " shows that with respect to unsubstituted 1,2,3,4-tetralin, alkyl replaces makes the molar absorptivity response factor reduce about 20%.
Confirm aromatic substance by NMR
The weight percent of the molecule with aromatic functionality in single aromatics standard substance of described purifying passes through long duration (long duration)
13The CNMR analysis confirmation.NMR is than the easier calibration of HPLC UV, because it measures aromatics carbon simply, so its response does not rely on the kind of analyzed aromatic substance.Aromatic substance by the 95-99% in the saturated lubricant base oil of known altitude is a monocyclic aromatics, and NMR result is converted into % aromatic molecules (for consistent with HPLC-UV and D2007) from % aromatics carbon.
The baseline analysis that needs high ability (high power), long duration to become reconciled is accurately to measure the aromatic substance that is low to moderate 0.2% aromatic molecules.
More specifically, in order accurately to measure low-level all molecules with at least one aromatic functionality by NMR, the D5292-99 method of standard is modified with the minimum carbon susceptibility that provides 500: 1 (by ASTM standard program E386).The operation of the 15 hour time length of employing on 400-500MHz NMR with 10-12mm Nalorac probe.Use Acorn PC integration software to define the shape of baseline and integration as one man.Being in operation changes the primary carrier frequency, to avoid being derived from the non-natural sign of aliphatic peak in the imaging in aromatics zone.By taking the photograph spectrum in the both sides of described carrier wave spectrum, resolving power is significantly improved.
The naphthenic hydrocarbon of measuring by FIMS distributes
It is more stable to oxidation than naphthenic hydrocarbon that paraffinic hydrocarbons is considered to, and therefore paraffinic hydrocarbons is more wished.Monocycle alkane is considered to more stable to oxidation than polycyoalkane.Yet when all have at least one cycloalkanes and belong to the weight percent of molecule of functionality when very low in the lubricant base oil, additive solubleness is low and elastomer compatibility is poor.Example with base oil of these character is polyalphaolefin and has Fischer-Tropsch base oil (GTL base oil) less than about 5% naphthenic hydrocarbon.In order in finished lubricants, to improve these character, must often add for example ester class of expensive cosolvent.Preferably, the Fischer-tropsch derived lubricant base oil that uses in the finished lubricants of the lubricant of blending of the present invention and blending comprises the molecule that polynaphthene belongs to functionality that has that mononaphthene belongs to the molecule of functionality and low weight percentage that has of high weight percent, so that described Fischer-tropsch derived lubricant base oil has high oxidative stability and high viscosity index and good additive solubleness and elastomer compatibility, and the finished lubricants of the lubricant of therefore described blending and blending has high oxidative stability and high viscosity index and good additive solubleness and elastomer compatibility.
Use field ion mass spectrum (FIMS) to measure to have that cycloalkanes belongs to and polynaphthene belongs to the composition of the molecule of functionality.On VG 70VSE mass spectrograph, obtain the FIMS spectrum.Sample imports via the solid probe, and this solid probe is heated to 500 ℃ by the speed with 50 ℃/min from about 40 ℃.Described mass spectrograph scans m/z1000 with 5 seconds/10 speed from m/z40.With the mass spectrum that obtains add and, to produce " average " spectrogram.The software package that use derives from PC-MassSpec carries out the C13 correction to each spectrogram.Use that the paraffinic hydrocarbons of purified branching almost and height cycloalkanes belong to, the concoction of the basic raw material of aromatic-containing compound is not estimated the FIMS Ionization Efficiency.Isoparaffin in these base oils is identical with the Ionization Efficiency of naphthenic hydrocarbon basically.Isoparaffin and naphthenic hydrocarbon account for more than 99.9% of saturates in the lubricant base oil of the present invention.The response factor of supposing all types of compounds is 1.0, so directly provide weight percent from area percentage.
Lubricant base oil of the present invention is characterized into paraffinic hydrocarbons and the molecule with different degree of unsaturation values by FIMS.Described molecule with different degree of unsaturation values can be made up of naphthenic hydrocarbon, alkene and aromatic substance.Because lubricant base oil of the present invention has the very aromatic substance and the alkene of low levels, described molecule with different degree of unsaturation values can be construed as the naphthenic hydrocarbon of the ring with different numbers.Therefore, for lubricant base oil of the present invention, 1-degree of unsaturation thing is a monocycle alkane, 2-degree of unsaturation thing is a bicyclic alkane, and 3-degree of unsaturation thing is three naphthenic hydrocarbon, and 4-degree of unsaturation thing is a Fourth Ring alkane, 5-degree of unsaturation thing is that five rings alkane and 6-degree of unsaturation thing are six naphthenic hydrocarbon.If aromatic substance exists in the lubricant base oil with significant amount, they will be accredited as 4-degree of unsaturation thing in FIMS analyzes.The summation of the 2-degree of unsaturation thing in white oil of the present invention, 3-degree of unsaturation thing, 4-degree of unsaturation thing, 5-degree of unsaturation thing and 6-degree of unsaturation thing is to have the weight percent that polynaphthene belongs to the molecule of functionality.The summation of the 1-degree of unsaturation thing in lubricant base oil of the present invention is to have the weight percent that mononaphthene belongs to the molecule of functionality.
In one embodiment, described Fischer-tropsch derived lubricant base oil has greater than 10wt%, is preferably greater than 15wt%, more preferably greater than the molecule that cycloalkanes belongs to functionality that has of 20wt%.They have greater than 15, are preferably greater than 50, more preferably greater than 100 have mononaphthene belong to functionality molecule weight percent with have polynaphthene and belong to the ratio of weight percent of the molecule of functionality.In preferred embodiments, described Fischer-tropsch derived lubricant base oil has the molecule that mononaphthene belongs to functionality that has greater than 10wt%, with the molecule that polynaphthene belongs to functionality that has, or even do not have a molecule that polynaphthene belongs to functionality less than 0.1wt%.In this embodiment, described Fischer-tropsch derived lubricant base oil can be between about 2cSt and about 20cSt, preferably between about 2cSt and about 12cSt, most preferably between about 3.5cSt and about 12cSt 100 ℃ kinematic viscosity.
In another embodiment, in described Fischer-tropsch derived lubricant base oil, have between the kinematic viscosity that at least one cycloalkanes belongs to the weight percent of molecule of functionality and lubricant base oil of the present invention at all and to have a kind of relation.That is, 100 ℃ be that the kinematic viscosity of unit is high more with cSt, it is resulting that to have the amount of molecule that cycloalkanes belongs to functionality high more.In a preferred embodiment, have the weight percent that cycloalkanes belongs to the molecule of functionality in the described Fischer-tropsch derived lubricant base oil and take advantage of 3, be preferably greater than 15, more preferably greater than 20 greater than the kinematic viscosity that with cSt is unit; And have mononaphthene belong to functionality molecule weight percent with have the ratio of weight percent of molecule that polynaphthene belongs to functionality greater than 15, be preferably greater than 50, more preferably greater than 100.Described Fischer-tropsch derived lubricant base oil 100 ℃ kinematic viscosity between about 2cSt and about 20cSt, preferably between about 2cSt and about 12cSt.The example of these base oils can have 100 ℃ of kinematic viscosity between about 2cSt and about 3.3cSt, and has high weight percent but less than the molecule that cycloalkanes belongs to functionality that has of 10wt%.
" the Influence of Group II﹠amp that in the 1999 AIChE spring whole nation meetings of March 16 in 1999, submits to by people such as D.C.Kramer at Houston; III Base OilComposition on VI and Oxidation Stability " in the ASTM D5292-99 and the HPLC-UV testing method of the modification that is used to test the low levels aromatic substance and the FIMS testing method that is used to characterize saturates have been described, the content of described document integral body by reference is combined in herein.
Although described Fischer-Tropsch wax raw material is substantially free of alkene, the base oil process technology may be introduced alkene because of " cracking " reaction, particularly at high temperature.In the presence of heat or UV-light, alkene can polymerization, forms more high-molecular weight product, and this may make base oil painted or cause settling.Usually, by hydrofining or by clay treatment, can remove alkene in the methods of the invention.
The character of the Fischer-tropsch derived lubricant base oil that uses among the embodiment is summarized in down Table III.
Table III: FTBO character
| FT-4A | FT-4B | FT-8B | |
| 100 ℃ viscosity (cSt) | 3.94 | 4.415 | 7.953 |
| Viscosity index | 143 | 147 | 165 |
| Pour point (℃) | -19 | -12 | -12 |
| FIMS analyzes % alkane % monocycle alkane % polycyoalkane and amounts to | 89.0 11.0 0.0 100.0 | 89.1 10.9 0.0 100.0 | 87.2 12.6 0.2 100.0 |
In the different stable hydrocarbon of being found in lubricant base oil, paraffinic hydrocarbons is considered to more stable to oxidation than naphthenic hydrocarbon (naphthene) traditionally, and therefore paraffinic hydrocarbons is more wished.Yet when the amount of aromatic substance in the base oil during less than 1wt%, the valid approach of further improving oxidative stability is the viscosity index that increases described base oil.Fischer-tropsch derived lubricant base oil generally contains the aromatic substance less than 1%.Because the utmost point low levels of aromatic substance and polycyclic naphthene hydrocarbon in the Fischer-tropsch derived lubricant base oil of the present invention, their high oxidation stability is considerably beyond the oxidative stability of traditional lubricant base oil.In addition, Fischer-tropsch derived lubricant base oil generally is classified as API III group base oil, and has low sulfur content, the saturates content greater than 95%, high viscosity index (HVI) and excellent cold flow character less than 5ppm.
Can be used for Fischer-tropsch derived lubricant base oil of the present invention and have high viscosity index.Measure viscosity index by ASTM D2270-93 (98).Usually, they have the viscosity index greater than 120, preferably have the viscosity index greater than the amount of calculating by following formula: viscosity index=28 * Ln (100 ℃ kinematic viscosity)+95 more preferably has the viscosity index greater than the amount of calculating by following formula: viscosity index=28 * Ln (100 ℃ kinematic viscosity)+105.
The lubricant base oil of blending
The lubricant base oil of blending of the present invention comprises 〉=and the Fischer-tropsch derived lubricant base oil of 70wt% and at least a kinematic viscosity at 100 ℃ is greater than about 30cSt and less than the polyalphaolefin lubricant base oil of 150cSt.The lubricant base oil of described blending preferably comprises the described at least a Fischer-tropsch derived lubricant base oil of the about 99wt% of 70-and the described at least a polyalphaolefin of about 1-30wt%.Can prepare the lubricant base oil of described blending by concoct described Fischer-tropsch derived lubricant base oil and described polyalphaolefin lubricant base oil with technology well known by persons skilled in the art.
Described Fischer-tropsch derived lubricant base oil 100 ℃ kinematic viscosity between about 2cSt and about 20cSt, preferably between about 2cSt and about 12cSt.Preferably, the difference of 100 ℃ of kinematic viscosity of described Fischer-tropsch derived lubricant base oil and described polyalphaolefin lubricant base oil is greater than 40cSt, more preferably greater than 70cSt.
For the finished lubricants of blending is provided, the lubricant base oil of described blending mixes with at least a wear preventive additive.Can prepare the finished lubricants of described blending by lubricant base oil and the described wear preventive additive of concocting described blending with technology well known by persons skilled in the art.From each component (being described Fischer-tropsch derived lubricant base oil, described polyalphaolefin lubricant base oil and described wear preventive additive), the finished lubricants component of described blending can be concocted in one step, and the finished lubricants of described blending directly is provided.In alternative method, can at first described Fischer-tropsch derived lubricant base oil and described polyalphaolefin lubricant base oil be concocted so that the lubricant of blending to be provided, the lubricant of described blending can former state mix with wear preventive additive then.The lubricant of described blending is can former state separated, perhaps can carry out the interpolation of wear preventive additive at once.
The Fischer-tropsch derived lubricant base oil that uses in the finished lubricants of the lubricant base oil of blending of the present invention and blending can be made in different place, the place that is received and concocts with the component of the lubricant of described blending.In addition, can make the finished lubricants of described blending in different place, the place that is received and concocts with the component of the lubricant base oil of described blending.Preferably, make the lubricant base oil of described blending and the finished lubricants of described blending in same place, this place is different from the initial manufactured place of described Fischer-tropsch derived lubricant base oil.Correspondingly, described Fischer-tropsch derived lubricant base oil is manufactured in first place, and is transported to the second remote place.This second remote place receives described Fischer-tropsch derived lubricant base oil, described polyalphaolefin and described additive, and makes the finished lubricants of described blending in this second place.
The finished lubricants of blending
Finished lubricants comprises at least a lubricant base oil and at least a additive.Lubricant base oil is the most important component of finished lubricants, generally account for finished lubricants 〉=70%.Finished lubricants of the present invention can be used to automobile, diesel motor, wheel shaft, wheel box and industrial application.
The finished lubricants of blending of the present invention comprises at least a Fischer-tropsch derived lubricant base oil, at least a kinematic viscosity is greater than about 30cSt and less than the polyalphaolefin lubricant base oil of 150cSt, with at least a wear preventive additive of significant quantity, described Fischer-tropsch derived lubricant base oil comprises 〉=6wt% have that mononaphthene belongs to the molecule of functionality and less than the molecule of 0.05wt% with aromatic functionality.The finished lubricants of blending of the present invention shows outstanding friction and abrasion resisting character.
Usually, in the finished lubricants that comprises Fischer-tropsch derived lubricant base oil the significant quantity of required wear preventive additive less than the amount of desired wear preventive additive in the finished lubricants that is comprising traditional petroleum lubricant base oil or polyalphaolefin lubricant base oil.According to the present invention, surprisingly find: comprise with the Fischer-tropsch derived lubricant base oil of polyalphaolefin lubricant base oil (its 100 ℃ kinematic viscosity greater than about 30cSt and less than 150cSt) blending (it comprises 〉=6wt% have that mononaphthene belongs to the molecule of functionality and less than the molecule of 0.05wt% with aromatic functionality) finished lubricants, than comprising Fischer-tropsch derived lubricant base oil but do not comprise the remarkable wear preventive additive still less of finished lubricants needs of polyalphaolefin lubricant base oil.Therefore, in the finished lubricants of blending of the present invention, need the wear preventive additive of reduction.Like this, the lubricant of blending of the present invention can be used to prepare high-quality engine oil and other finished lubricants that satisfies the strictest modern engine oil technical specifications.
The significant quantity of at least a wear preventive additive is meant in the lubricant base oil that joins described blending in additive-package or separately the amount with the wear preventive additive of the finished lubricants that a kind of blending is provided, the finished lubricants of described blending is 1, have less than 300 under the load that 000g applies, 000 cu, preferably less than 170,000 cu is more preferably less than the HFRR wear volume of 150,000 cus.Even more preferably, the finished lubricants of described blending has the HFRR wear volume less than 110,000 cus 1 under the load that 000g applies.According to the present invention, the significant quantity of at least a wear preventive additive is preferably between about 0.001 and 5wt% of the finished lubricants of described blending.The significant quantity of the wear preventive additive in the finished lubricants of blending of the present invention is less than comprising Fischer-tropsch derived lubricant base oil but do not contain the lubricant of polyalphaolefin lubricant base oil and comprise the polyalphaolefin lubricant base oil but do not contain the significant quantity of desired wear preventive additive in the lubricant of Fischer-tropsch derived lubricant base oil.
Chemical reaction takes place in the metallic surface of wear preventive additive and lubricated equipment, to be formed on the layer that is low to moderate under moderate temperature and the load or reduces wear under high temperature and load.Usually, described metallic surface comprises iron alloy.Described wear preventive additive can be one or more metal phosphates, metal dithionite for phosphoric acid salt, metal dialkyl dithiophosphates, metal thiocarbamate, metal dithionite for the dialkyl dithiophosphate of carbaminate, metal dialkyl dithiocar-bamate, ethoxylated amine, the dithiobenzoic acid salt of ethoxylated amine, neutral organophosphite, organic molybdenum, organosulfur compound, sulphur compound, chlorine compound, or their mixture.Preferably, described wear preventive additive is the metal dialkyl dithiophosphates, and even more preferably, described metal is a zinc.McDonald, R.A. and Phillips, W.D., " Lubricant Additives Chemistry andApplication ", the 2nd Zhanghe the 3rd chapter (2003) has provided the summary of dissimilar wear preventive additives.
The finished lubricants of blending of the present invention can further comprise other additive, for example extreme-pressure additive (EP agent), purification agent, dispersion agent, antioxidant, pour point depressor, viscosity index improver, ester cosolvent, viscosity modifier, friction improver, emulsion splitter, defoamer, inhibiter, rust-preventive agent, sealed expander, emulsifying agent, wetting agent, lubricity improver, metal passivator, jelling agent, tackiness agent, sterilant, anti-liquid loss additive, tinting material and their combination.
When adding viscosity index improver, preferably they exist with the amount less than 8wt%, and when adding the ester cosolvent, preferably they exist with the amount less than 3wt%.Even more preferably, finished lubricants of the present invention does not comprise viscosity index improver or ester cosolvent.Preferably, under the situation of not using any viscosity index improver, the finished lubricants of blending of the present invention has greater than 140, the viscosity index more preferably greater than 165.
Finished lubricants of the present invention can be re-dubbed crank case of internal combustion engine oil, gear box oil, power train fluid, turbine oil, compressor oil, hydraulic efficiency oil or the lubricating grease of many grades.In one embodiment, the finished lubricants of described blending is the many grades crank case of internal combustion engine oil that satisfies the SAE J300 specification in June calendar year 2001.In a specific embodiments, the finished lubricants of described blending is to satisfy many grades crank case of internal combustion engine oil of specification that viscosity grade is the engine oil of 0W-20,5W-XX, 10W-XX or 15W-XX, and wherein XX is 20,30,40,50 or 60.In another embodiment, the finished lubricants of described blending is the many grades crank case of internal combustion engine oil that satisfies the specification of at least a ACEA 2002 European oil product sequences that are used for petrol engine, light-duty diesel engine or heavy duty diesel engine.
Many grades crank case of internal combustion engine oil of the present invention preferably has and is less than or equal to the total settling weight of about 45 milligrams TEOST-MHT.
Surprisingly, the finished lubricants of blending of the present invention has shown outstanding friction and abrasion resisting character, although require the wear preventive additive of reduction.The finished lubricants of blending of the present invention reduces the wearing and tearing in the equipment of being made by iron alloy.Iron alloy is the alloy that contains the iron of different carbon, manganese and one or more other elements such as sulphur, nickel, silicon, phosphorus, chromium, molybdenum and the vanadium of measuring.When combining with iron, these elements form the dissimilar steel of different nature that has.Wear preventive additive is designed to and metallic surface (being generally iron alloy surface) reaction, to reduce the wearing and tearing when lip-deep uneven place contacts with each other.
When the finished lubricants of described blending is re-dubbed the crank case of internal combustion engine oil of many grades; by using fuels run engine and the finished lubricants lubricating engine that uses the blending of claimed invention here, can turn round comprises the oil engine of valve mechanism.Described engine can be a self-igniton engine, perhaps more specifically, can be the self-igniton engine of being furnished with exhaust aftertreatment device.Described engine can be the engine of spark ignition, perhaps more specifically, can be the engine of being furnished with the spark ignition of exhaust aftertreatment device.Described engine can further be equipped with turbo-supercharger.Described fuel can be diesel-fuel, low-sulfur diesel fuels, Fuel Petroleum, white gasoline or Sweet natural gas.
Embodiment
Further explain the present invention by following exemplary embodiment, described embodiment is nonrestrictive.
Embodiment 1:
The preparation of Fischer-Tropsch wax and Fischer-tropsch derived lubricant base oil
Use the Fischer-Tropsch wax sample of two hydrotreatments of co-based fischer-tropsch Preparation of Catalyst, i.e. FT wax A and FT wax B.Analyze two samples, find that they have the character shown in the Table V.
Table V: Fischer-Tropsch wax
| Fischer-tropsch catalysts | Cobalt-based | Cobalt-based |
| Fischer-Tropsch wax | FT wax A | FT wax B |
| Sulphur, ppm | ＜6 | 7，＜2 |
| Nitrogen, ppm | 6，5 | 12，19 * |
| By the oxygen that NA measures, wt% | 0.59 | 0.69 |
| The gas-chromatography normal paraffin is analyzedTotal normal paraffin, wt% average carbon number molecular-weight average | 84.4727.3384.9 | 83.7230.7432.5 |
| D-6352 SIMDIST TBP(WT％)，T 0.5T 5T 10T 20T 30T 40T 50T 60T 70T 80T 90T 95T 99.5 | 515597639689714751774807839870911935978 | 12956862567471775679282787391496510051090 |
| T 90-T 10，℃ | 133 | 171 |
| Wt％C 30+ | 34.69 | 40.86 |
| Wt％C 60+ | 0.00 | 0.00 |
| C 60+/C 30+ | 0.00 | 0.00 |
* have more than the result of a value is the result of repeated test.
Described Fischer-Tropsch synthetic crude has less than 0.18 the compound with at least 60 carbon atoms and has the weight ratio and the T between 900 and 1000 of the compound of at least 30 carbon atoms
90Boiling point.3 Fischer-Tropsch wax samples of hydroisomerization (a FT wax A sample and two FT wax B samples) on based on the Pt/SSZ-32 catalyzer of alumina binder or Pt/SAPO-11 catalyzer.Operational condition comprises: the temperature between 652 and 695 , 0.6-1.0hr
-1LHSV, the reactor pressure of 1000psig, and 6 and 7MSCF/bbl between one way hydrogen speed.Reactor effluent directly leads to second reactor that contains the Pt/Pd Hydrobon catalyst that loads on the silica-alumina, and this second reactor is also operated under 1000psig.The condition of this second reactor comprises temperature and the 1.0hr of 450
-1LHSV.
Be higher than the product of 650 by normal pressure or vacuum distilling fractionation boiling point, to produce the overhead product cut of different viscosity grade.Obtain three kinds of Fischer-tropsch derived lubricant base oil: FT-4A (coming from FT wax A) and FT-4B and FT-8B (the two all comes from FT wax B).Test data to the concrete overhead product cut that can be used as Fischer-tropsch derived lubricant base oil is shown in down Table VI.
Table VI: Fischer-tropsch derived lubrication base oil properties
| Character | FT-4A | FT-4B | FT-8B |
| The hydroisomerization temperature, | 672 | 700 | 694 |
| The hydroisomerization dewaxing catalyst | Pt/SAPO-11 | Pt/SAPO-11 | Pt/SAPO-11 |
| Reactor pressure, psig | 1000 | 1000 | 1000 |
| 100 ℃ viscosity, cSt | 3.94 | 4.415 | 7.953 |
| Viscosity index | 143 | 147 | 165 |
| Aromatic substance, wt% | 0.004 | 0.008 | 0.006 |
| FIMS, the wt% paraffinic hydrocarbons monocycle alkane polycyoalkane of molecule amounts to | 89.011.00.0100.0 | 89.1 10.9 0.0 100.0 | 87.2 12.6 0.2 100.0 |
| Api gravity | 42.0 | 41.6 | 39.62 |
| Pour point, ℃ | -19 | -12 | -12 |
| Cloud point, ℃ | -9 | -8 | +13 |
| The ratio of monocycle/polycyoalkane | ＞100 | ＞100 | 61 |
| The ratio of pour point/100 ℃ viscosity (SMA considers to remove) | -4.82 | -2.72 | -1.51 |
| Base oil is toppled over the factor | -7.92 | -7.09 | -2.76 |
| Oxidizer BN, hour | No data | 41.35 | No data |
| The Noack volatility, wt% | 14.6 | 10.89 | 2.72 |
| -35 ℃ CCS viscosity, cP | 1611 | 2079 | 13627 |
The ratio of the kinematic viscosity of pour point and 100 ℃ only be in ℃ pour point removed by 100 ℃ kinematic viscosity.It is the empirical value that calculates by following formula that base oil is toppled over the factor:
Base oil is toppled over the factor=7.35 * Ln (100 ℃ kinematic viscosity)-18,
Wherein Ln (100 ℃ kinematic viscosity) is to be the natural logarithm at the end in 100 ℃ of kinematic viscosity of cSt with " e ".
Embodiment 2:
The preparation of the finished lubricants of blending
The Fischer-tropsch derived lubricant base oil for preparing above (FT-4A, FT-4B and FT-8B) is used to prepare the finished lubricants of blending.
Several polyalphaolefins (PAO) with 100 ℃ of different kinematic viscosity also are used to prepare the finished lubricants of described blending.Employed PAO is as follows: Chevron Phillips PAO-4, PAO-8 and PAO-25; Durasyn
174 PAO-40 (Durasyn
Be the registered trademark of Amoco chemical company); With Mobil SHF-1003 PAO-100.The described PAO of digitized representation in the PAO identification (being PAO-100) 100 ℃ be the kinematic viscosity of unit with cSt.
(concoction that will contain Fischer-tropsch derived lubricant base oil and high viscosity PAO (PAO-40 or PAO-100) is re-dubbed standard passenger vehicle engine oil for Detergent-Inhibitor, DI) additive-package and pour point depressor (PPD) with purification agent-inhibitor.In described concoction, do not add viscosity index improver,, and therefore need not add any viscosity index improver because viscosity index is very high.Use HFRR to carry out friction and wear on test oil and measure, low HFRR frictional coefficient is general relevant with good fuel economy.Test result to these concoctions is shown in Table VII.
Table VII: the Fischer-Tropsch base oil (FTBO) of very low wearing and tearing and the concoction of high viscosity PAO
| Describe | 0W-20 | 10W-30 |
| Wt％FT-4A | 73.36 | 0 |
| Wt％FT-8B | 0 | 78.5 |
| Wt％Mobil SHF-1003 PAO-100 | 0 | 10.85 |
| Wt％Durasyn 174 PAO-40 | 15.99 | 0 |
| The Wt%DI additive-package | 10.35 | 10.35 |
| Wt％PPD | 0.3 | 0.3 |
| CCS(cP) | 4100, at-35 ℃ | 6360, at-25 ℃ |
| 100 ℃ of viscosity (cSt) | 7.093 | 12.54 |
| Viscosity index | 170 | 172 |
| Noack volatility (Wt%) | 14.36 | 3.65 |
| MRV(cP) | 8442, at-40 ℃ | 228879-YS is at-30 ℃ |
| Oxidizer B, the L-4 catalyzer (hour) | Do not survey | 30.04 |
| At 150 ℃ HTHS (cP) | 2.22 | 3.93 |
| TEOST MHT(mg) | 33.3 | 54.2 |
| The HFRR frictional coefficient | 0.111 | 0.104 |
| Wear volume under the HFRR plane (cu) | 148645 | 109779 |
| The clean wear volume of HFRR (cu) | -1600 | 20086 |
YS refers to the existence of yielding stress in the MRV test.
Above digital proof 〉=70wt% contains 〉=and 6wt% has low wearing and tearing and the excellent oxidative stability (the oxidizer B with L-4 catalyzer) that mononaphthene belongs to the concoction of the Fischer-tropsch derived lubricant base oil (FT-4A and FT-8B) of the molecule of functionality and high viscosity PAO (PAO-40 and PAO-100).Have minimum HFRR frictional coefficient and minimum HFRR plane down the concoction of wearing and tearing be 〉=70wt% contains 〉=6wt% has mononaphthene and belong to the Fischer-tropsch derived lubricant base oil of molecule of functionality and the concoction of high viscosity PAO, the difference of 100 ℃ of kinematic viscosity of wherein said Fischer-tropsch derived lubricant base oil and PAO is greater than 70cSt.
By comparison, as in Table VIII, seeing, ≤ 70wt% contains 〉=and 6wt% has the Fischer-tropsch derived lubricant base oil (concoction of FT-4A or FT-4B) and low viscosity PAO (PAO-8 and PAO-25) or high viscosity PAO (PAO-100) that mononaphthene belongs to the molecule of functionality, have excellent friction and abrasion resisting character, but do not show from comprise 〉=the Fischer-tropsch derived lubricant base oil of 70wt% and 100 ℃ of kinematic viscosity is greater than about 30cSt and less than the friction and wear benefit of the concoction visible raising of the present invention of the PAO (PAO-40 and PAO-100) of 150cSt.
The comparison concoction of Table VIII: FT and PAO
| Describe | 0W-20 | 0W-20 | 5W-30 |
| Wt％FT-4A | 31.83 | 69.87 | 0 |
| Wt％FT-4B | 0 | 0 | 66.15 |
| Wt％Chevron Phillips PAO-8 | 57.52 | 0 | 0 |
| Wt％Chevron Phillips PAO-25 | 0 | 19.47 | 0 |
| Wt％Mobil SHF-1003 PAO-100 | 0 | 0 | 23.2 |
| The Wt%DI additive-package | 10.35 | 10.35 | 10.35 |
| Wt％PPD | 0.3 | 0.3 | 0.3 |
| CCS(cP) | 5534, at-35 ℃ | 3876, at-35 ℃ | 5993, at-30 ℃ |
| 100 ℃ of viscosity (cSt) | 7.555 | 6.981 | 11.32 |
| Viscosity index | 145 | 169 | 161 |
| Noack volatility (Wt%) | 7.19 | 13.77 | 9.6 |
| MRV(cP) | 11768, at-40 ℃ | 9600, at-40 ℃ | 13207, at-35 ℃ |
| Oxidizer B, the L-4 catalyzer (hour) | 28.82 | Do not survey | 23.29 |
| At 150 ℃ HTHS (cP) | 2.32 | 2.41 | 3.58 |
| TEOST MHT(mg) | 28.7 | 25.9 | 28.5 |
| The HFRR frictional coefficient | 0.116 | 0.115 | 0.111 |
| Wear volume under the HFRR plane (cu) | 187885 | 182030 | 172120 |
| The clean wear volume of HFRR (cu) | 55510 | 35960 | 29425 |
Prepare two 0W-20 concoctions, one has full FTBO prescription, and one has full PAO prescription.These concoctions are carried out the HFRR wear testing for comparing.Test result to these samples is presented among the Table I X.
Table I X:
The comparison concoction of full FTBO and full PAO
| Describe | Full FTBO 0W-20 | Full PAO 0W-20 |
| Wt％FT-4B | 53.74 | 0 |
| Wt％FT-8B | 35.61 | 0 |
| Wt％Chevron Phillips PAO-4 | 0 | 31.83 |
| Wt％Chevron Phillips PAO-8 | 0 | 57.52 |
| The Wt%DI additive-package | 10.35 | 10.35 |
| Wt％PPD | 0.3 | 0.3 |
| CCS(cP) | 5660, at-35 ℃ | 5534, at-35 ℃ |
| 100 ℃ of viscosity (cSt) | 7.09 | 7.555 |
| Viscosity index | 167 | 145 |
| Noack volatility (Wt%) | 8.86 | 7.19 |
| MRV(cP) | Failure (71156) at-40 ℃ | 11768, at-40 ℃ |
| Oxidizer B, the L-4 catalyzer (hour) | 28.7 | 28.82 |
| At 150 ℃ HTHS (cP) | 2.36 | 2.3 |
| TEOST MHT(mg) | 40 | 28.7 |
| The HFRR frictional coefficient | 0.110 | 0.116 |
| Wear volume under the HFRR plane (cu) | 170340 | 180560 |
| The clean wear volume of HFRR (cu) | 30190 | 38975 |
Although these comparative results prove holder deutero-lubricant base oil concoction in full and provide better nature of friction and lower wearing and tearing than full PAO concoction, but find: compare with holder deutero-lubricant base oil concoction in full, the concoction that the mixture by Fischer-tropsch derived lubricant base oil of 〉=70wt% and viscosity higher PAO (PAO-100) of identical viscosities grade (0W-20) is formed has remarkable lower wearing and tearing.Surprisingly, describedly have 〉=concoction of the mixture of 70wt% Fischer-Tropsch lubricant base oil and high viscosity PAO provides the minimizing of wear volume under the HFRR plane of 12.7% (0W-20) and 35.6% (10W-30).
Although described the present invention in conjunction with specific embodiment, the application attempts to contain those the different variations that can be made by those of ordinary skills and substitutes under the situation of the spirit and scope that do not depart from appended claims.
Claims (29)
1. Tiao He lubricant base oil, the lubricant base oil of this blending comprises:
A. 〉=the Fischer-tropsch derived lubricant base oil of 70wt%, it comprises 〉=6wt% have that mononaphthene belongs to the molecule of functionality and less than the molecule of 0.05wt% with aromatic functionality; With
B. at least a polyalphaolefin lubricant base oil, its 100 ℃ kinematic viscosity greater than about 30cSt and less than 150cSt.
2. the lubricant base oil of the blending of claim 1, wherein said Fischer-tropsch derived lubricant base oil comprises the molecule that cycloalkanes belongs to functionality that has greater than 10wt%, and have mononaphthene belong to functionality molecule weight percent with have polynaphthene and belong to the ratio of weight percent of molecule of functionality greater than 15.
3. the lubricant base oil of the blending of claim 1, wherein said Fischer-tropsch derived lubricant base oil comprises the molecule with aromatic functionality less than 0.01wt%.
4. the lubricant base oil of the blending of claim 1, wherein said Fischer-tropsch derived lubricant base oil comprise 〉=10wt% have a molecule that mononaphthene belongs to functionality.
5. the lubricant base oil of the blending of claim 1, the difference of 100 ℃ of kinematic viscosity of wherein said Fischer-tropsch derived lubricant base oil and described polyalphaolefin lubricant base oil is greater than 40cSt.
6. the lubricant base oil of the blending of claim 5, the difference of 100 ℃ of kinematic viscosity of wherein said Fischer-tropsch derived lubricant base oil and described polyalphaolefin lubricant base oil is greater than 70cSt.
7. Tiao He finished lubricants, the finished lubricants of this blending comprises:
A. 〉=the Fischer-tropsch derived lubricant base oil of 70wt%, it comprises 〉=6wt% have that mononaphthene belongs to the molecule of functionality and less than the molecule of 0.05wt% with aromatic functionality;
B. at least a polyalphaolefin lubricant base oil, its 100 ℃ kinematic viscosity greater than about 30cSt and less than 150cSt; With
C. at least a wear preventive additive of significant quantity.
8. the finished lubricants of the blending of claim 7, wherein said Fischer-tropsch derived lubricant base oil comprise less than the molecule of 0.05wt% with aromatic functionality and 〉=10wt% have a molecule that cycloalkanes belongs to functionality, and have mononaphthene belong to functionality molecule weight percent with have polynaphthene and belong to the ratio of weight percent of molecule of functionality greater than 15.
9. the finished lubricants of the blending of claim 7, wherein said Fischer-tropsch derived lubricant base oil comprises the molecule with aromatic functionality less than 0.01wt%.
10. the finished lubricants of the blending of claim 7, wherein said Fischer-tropsch derived lubricant base oil comprise 〉=8wt% have a molecule that mononaphthene belongs to functionality.
11. the finished lubricants of the blending of claim 10, wherein said Fischer-tropsch derived lubricant base oil comprise 〉=10wt% have a molecule that mononaphthene belongs to functionality.
12. the finished lubricants of the blending of claim 7, the significant quantity of wherein said at least a wear preventive additive 0.001 and the scope of 5wt% in.
13. the finished lubricants of the blending of claim 7, the finished lubricants of wherein said blending have about 2.0 and 20cSt between 100 ℃ of kinematic viscosity.
14. the finished lubricants of the blending of claim 7, the finished lubricants of wherein said blending have the Noack volatility less than 12wt%.
15. the finished lubricants of the blending of claim 7, the finished lubricants of wherein said blending have the oxidizer B test result that contains the L-4 catalyzer greater than 22 hours.
16. having, the finished lubricants of the blending of claim 7, the finished lubricants of wherein said blending be less than or equal to the total settling weight of about 45 milligrams TEOST-MHT.
17. the finished lubricants of the blending of claim 7, the finished lubricants of wherein said blending has the viscosity index greater than 165.
18. the finished lubricants of the blending of claim 7, the finished lubricants of wherein said blending show wear volume under the HFRR plane that is less than or equal to 300,000 cus.
19. the finished lubricants of the blending of claim 7, wherein said at least a wear preventive additive is selected from the group that following material is formed: metal phosphate, metal dithionite for phosphoric acid salt, metal dialkyl dithiophosphates, metal thiocarbamate, metal dithionite for the dialkyl dithiophosphate of carbaminate, metal dialkyl dithiocar-bamate, ethoxylated amine, dithiobenzoic acid salt, neutral organophosphite, organic molybdenum, organosulfur compound, sulphur compound, chlorine compound and their mixture of ethoxylated amine.
20. the finished lubricants of the blending of claim 7, also comprise at least a other lubricant additive, described other lubricant additive is selected from the group that following material is formed: extreme-pressure additive, purification agent, dispersion agent, antioxidant, pour point depressor, viscosity index improver, the ester cosolvent, viscosity modifier, friction improver, emulsion splitter, defoamer, inhibiter, rust-preventive agent, sealed expander, emulsifying agent, wetting agent, lubricity improver, metal passivator, jelling agent, tackiness agent, sterilant, anti-liquid loss additive, tinting material and their mixture.
21. the finished lubricants of the blending of claim 20, wherein said finished lubricants are crank case of internal combustion engine oil, gear box oil, power train fluid, turbine oil, compressor oil, hydraulic efficiency oil or the lubricating grease of many grades.
22. the finished lubricants of the blending of claim 21, the finished lubricants of wherein said blending are the many grades crank case of internal combustion engine oil that satisfies the SAE J300 specification in June calendar year 2001.
23. the finished lubricants of the blending of claim 22, wherein said crank case of internal combustion engine oil satisfies the specification that viscosity grade is the engine oil of 0W-20,5W-XX, 10W-XX or 15W-XX, and wherein XX is 20,30,40,50 or 60.
24. the finished lubricants of the blending of claim 22, wherein said crank case of internal combustion engine oil satisfy at least a specification that is used for the ACEA 2002 European oil product sequences of petrol engine, light-duty diesel engine or heavy duty diesel engine.
25. the finished lubricants of the blending of claim 7, the significant quantity of wherein said at least a wear preventive additive are less than comprising Fischer-tropsch derived lubricant base oil but do not contain the significant quantity of wear preventive additive in the finished lubricants of polyalphaolefin lubricant base oil.
26. the finished lubricants of the blending of claim 7, the significant quantity of wherein said at least a wear preventive additive are less than comprising the polyalphaolefin lubricant base oil but do not contain the significant quantity of wear preventive additive in the finished lubricants of Fischer-tropsch derived lubricant base oil.
27. running has the method for the oil engine of valve mechanism, this method comprises:
A. use the finished lubricants lubricating engine of the blending of claim 7; With
B. use the fuels run engine.
28. the method for claim 27, wherein said engine are self-igniton engine or spark ignition engine, and described fuel is diesel-fuel, low-sulfur diesel fuels, Fuel Petroleum, white gasoline or Sweet natural gas.
29. reduce the method for the wearing and tearing in the iron alloy equipment, this method comprises:
A. use the lubricated described equipment of finished lubricants of the blending of claim 7; With
B. at the described equipment of described lubricated back running.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/069,979 | 2005-03-03 | ||
| US11/069,979 US20060196807A1 (en) | 2005-03-03 | 2005-03-03 | Polyalphaolefin & Fischer-Tropsch derived lubricant base oil lubricant blends |
| PCT/US2006/007836 WO2006094264A2 (en) | 2005-03-03 | 2006-03-01 | Polyalphaolefin & fischer-tropsch derived lubricant base oil lubricant blends |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101160381A true CN101160381A (en) | 2008-04-09 |
| CN101160381B CN101160381B (en) | 2011-03-23 |
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|---|---|---|---|
| CN2006800124169A Expired - Fee Related CN101160381B (en) | 2005-03-03 | 2006-03-01 | Polyalphaolefin & fischer-tropsch derived lubricant base oil lubricant blends |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20060196807A1 (en) |
| JP (1) | JP2008531834A (en) |
| CN (1) | CN101160381B (en) |
| AU (1) | AU2006218432B2 (en) |
| BR (1) | BRPI0608263A2 (en) |
| GB (1) | GB2438131B (en) |
| NL (1) | NL1031298C2 (en) |
| WO (1) | WO2006094264A2 (en) |
| ZA (1) | ZA200707484B (en) |
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- 2006-03-01 BR BRPI0608263-7A patent/BRPI0608263A2/en not_active IP Right Cessation
- 2006-03-01 ZA ZA200707484A patent/ZA200707484B/en unknown
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- 2006-03-01 CN CN2006800124169A patent/CN101160381B/en not_active Expired - Fee Related
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| CN102803446A (en) * | 2009-06-24 | 2012-11-28 | 国际壳牌研究有限公司 | Lubricating Composition |
| CN103119142A (en) * | 2010-09-24 | 2013-05-22 | 陶氏环球技术有限责任公司 | Non-aromatic based antioxidants for lubricants |
| CN103119142B (en) * | 2010-09-24 | 2015-12-02 | 陶氏环球技术有限责任公司 | For the non-aromatic family antioxidant of lubricant |
| CN106459818A (en) * | 2014-04-25 | 2017-02-22 | 路博润公司 | Multigrade lubricating compositions |
| CN105296061A (en) * | 2015-11-24 | 2016-02-03 | 杭州力特油剂有限公司 | Lubricating grease |
| CN106190467A (en) * | 2016-07-12 | 2016-12-07 | 天津蓝新石油化工有限公司 | A kind of viscosity is the SN level gasoline engine oil of 10W/30 |
| CN106190471A (en) * | 2016-07-12 | 2016-12-07 | 天津蓝新石油化工有限公司 | A kind of viscosity is the preparation method of the SN level gasoline engine oil of 10W/30 |
| CN106118830A (en) * | 2016-07-12 | 2016-11-16 | 天津蓝新石油化工有限公司 | A kind of viscosity is the SN level gasoline engine oil of 0W/20 |
| CN106167728A (en) * | 2016-07-12 | 2016-11-30 | 天津蓝新石油化工有限公司 | A kind of viscosity is the preparation method of the SN level gasoline engine oil of 10W/40 |
| CN106167729A (en) * | 2016-07-12 | 2016-11-30 | 天津蓝新石油化工有限公司 | A kind of viscosity is the SN level gasoline engine oil of 0W/30 |
| CN106190466A (en) * | 2016-07-12 | 2016-12-07 | 天津蓝新石油化工有限公司 | A kind of viscosity is the preparation method of the SN level gasoline engine oil of 5W/40 |
| CN106190469A (en) * | 2016-07-12 | 2016-12-07 | 天津蓝新石油化工有限公司 | A kind of viscosity is the preparation method of the SN level gasoline engine oil of 5W/30 |
| CN106118827A (en) * | 2016-07-12 | 2016-11-16 | 天津蓝新石油化工有限公司 | A kind of viscosity is the preparation method of the SN level gasoline engine oil of 0W/40 |
| CN106190470A (en) * | 2016-07-12 | 2016-12-07 | 天津蓝新石油化工有限公司 | A kind of viscosity is the preparation method of the SN level gasoline engine oil of 5W/20 |
| CN106190465A (en) * | 2016-07-12 | 2016-12-07 | 天津蓝新石油化工有限公司 | A kind of viscosity is the preparation method of the SN level gasoline engine oil of 0W/20 |
| CN106190468A (en) * | 2016-07-12 | 2016-12-07 | 天津蓝新石油化工有限公司 | A kind of viscosity is the SN level gasoline engine oil of 5W/20 |
| CN106118828A (en) * | 2016-07-12 | 2016-11-16 | 天津蓝新石油化工有限公司 | A kind of viscosity is the preparation method of the SN level gasoline engine oil of 0W/30 |
| CN106244302A (en) * | 2016-07-12 | 2016-12-21 | 天津蓝新石油化工有限公司 | A kind of viscosity is the SN level gasoline engine oil of 0W/40 |
| CN106244303A (en) * | 2016-07-12 | 2016-12-21 | 天津蓝新石油化工有限公司 | A kind of viscosity is the SN level gasoline engine oil of 10W/40 |
| CN106244301A (en) * | 2016-07-12 | 2016-12-21 | 天津蓝新石油化工有限公司 | A kind of viscosity is the SN level gasoline engine oil of 5W/40 |
| CN106118829A (en) * | 2016-07-12 | 2016-11-16 | 天津蓝新石油化工有限公司 | A kind of viscosity is the SN level gasoline engine oil of 5W/30 |
| CN110023465A (en) * | 2017-04-05 | 2019-07-16 | Jxtg能源株式会社 | Oil gear and hydraulic fluid composition |
| CN110546246A (en) * | 2017-04-25 | 2019-12-06 | 国际壳牌研究有限公司 | Lubricating oil composition for internal combustion engine |
| CN109762631A (en) * | 2018-12-29 | 2019-05-17 | 广州科卢斯流体科技有限公司 | A kind of Ashless type performance vacuum pumps oil |
| CN112342071A (en) * | 2020-10-26 | 2021-02-09 | 中国石油化工股份有限公司 | Base oil composition with high HTHS performance and preparation method thereof |
| CN113088368A (en) * | 2021-04-21 | 2021-07-09 | 中国石油化工股份有限公司 | Air compressor oil composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA200707484B (en) | 2009-01-28 |
| NL1031298C2 (en) | 2007-06-06 |
| US20060196807A1 (en) | 2006-09-07 |
| NL1031298A1 (en) | 2006-09-06 |
| WO2006094264A2 (en) | 2006-09-08 |
| WO2006094264A3 (en) | 2007-10-25 |
| AU2006218432B2 (en) | 2011-06-09 |
| AU2006218432A1 (en) | 2006-09-08 |
| JP2008531834A (en) | 2008-08-14 |
| GB2438131A (en) | 2007-11-14 |
| BRPI0608263A2 (en) | 2010-11-16 |
| GB0716575D0 (en) | 2007-10-10 |
| GB2438131B (en) | 2010-01-13 |
| CN101160381B (en) | 2011-03-23 |
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